Pesticide composition comprising malononitrile compounds

ABSTRACT

The present invention relates to use of malononitrile compounds of formula (X):  
                 
 
     wherein R 1  and R 2  are the same or different and independently C 1 -C 5  (halo)-alkyl, C 1 -C 5  (halo)alkyloxy, C 2 -C 5  (halo)alkenyl, C 2 -C 5  (halo)alkynyl, hydrogen, or cyano; R 3  and R 4  are the same or different and independently C 1 -C 10  alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, or hydrogen, or R 3  and R 4  are taken together to form C 2 -C 6  (halo)alkylene or C 4 -C 6  (halo)alkenylene; R 5  is halogen, cyano, nitro, C 1 -C 4  (halo)alkyl, or the like; n is an integer of 0 to 4; R 6  is halogen, cyano, nitro, C 1 -C 4  (halo)alkyl, or the like; or R 5  and R 6  are taken together to form methylenedioxy; with the provisos that when R 6  is hydrogen, then n is an integer of 1 to 4 and that when n is 2 or more, then R 5 &#39;s are different from each other; as pesticides, and to pesticide compositions containing these compounds as active ingredients. The present invention makes it possible to effectively control pests such as insect pests, acarine pests, and nematode pests.

TECHNICAL FIELD

[0001] The present invention relates to pesticide compositionscomprising the malononitrile compounds as active ingredients and to useof certain malononitrile compounds as pesticides.

BACK GROUND ART

[0002] Against pests such as insect pests, acarine pests, and nematodepests, various pesticide compositions have been used so far for theircontrol. The conditions of pesticide compositions required havedrastically been changed, including the care of their effects on theenvironment and the acquisition of drug resistance by pests to becontrolled. Under such circumstances, there have been great demands forthe development of new pesticide compositions.

DISCLOSURE OF INVENTION

[0003] The present inventors have extensively studied to find compoundshaving excellent pest controlling activity. As a result, they have foundthat the malononitrile compounds of formula (X) as depicted below haveexcellent controlling activity against pests such as insect pests,acarine pests, and nematode pests, thereby reaching the presentinvention.

[0004] That is, the present invention provides a pesticide compositioncomprising malononitrile compounds of formula (X):

[0005] (hereinafter referred to as compound(s) (X))

[0006] wherein R¹ and R² are the same or different and independentlyC₁-C₅ (halo)alkyl, C₁-C₅ (halo)alkyloxy, C₂-C₅ (halo)alkenyl, C₂-C₅(halo)alkynyl, hydrogen, or cyano;

[0007] R³ and R⁴ are the same or different and independently C₁-C₁₀alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, or hydrogen, or R³ and R⁴ aretaken together to form C₂-C₆ (halo)alkylene or C₄-C₆ (halo)alkenylene;

[0008] R⁵ is halogen, cyano, nitro, C₁-C₄ (halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl;

[0009] n is an integer of 0 to 4;

[0010] R⁶ is hydrogen, halogen, cyano, nitro, C₁-C₄ (halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl;

[0011] or R⁵ and R⁶ are taken together to form methylenedioxy; with theprovisos that when R⁶ is hydrogen, then n is an integer of 1 to 4 andthat when n is 2 or more, then R⁵'s are the same or different from eachother; as an active ingredient.

[0012] The present invention also provides use of compounds (X) asactive ingredients and pest controlling methods by applying compounds(X) to pests or habitats of pests.

MODE FOR CARRYING OUT THE INVENTION

[0013] In the definition of substituents as used herein, each group hasthe following meaning:

[0014] The (halo)alkyl group refers to alkyl optionally substituted withhalogen for one or more than one hydrogen atoms.

[0015] The (halo)alkyloxy group refers to alkyloxy optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0016] The (halo)alkenyl group refers to alkenyl optionally substitutedwith halogen for one or more than one hydrogen atoms.

[0017] The (halo)alkynyl group refers to alkynyl optionally substitutedwith halogen for one or more than one hydrogen atoms.

[0018] The (halo)alkylene group refers to alkylene optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0019] The (halo)alkenylene group refers to alkenylene optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0020] The (halo)alkylthio group refers to alkylthio optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0021] The (halo)alkylsulfinyl group refers to alkylsulfinyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0022] The (halo)alkylsulfonyl group refers to alkylsulfonyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0023] The (halo)alkylcarbonyl group refers to alkylcarbonyl optionallysubstituted with halogen for one or more than one hydrogen atoms.

[0024] The (halo)alkyloxycarbonyl group refers to alkyloxycarbonyloptionally substituted with halogen for one or more than one hydrogenatoms.

[0025] The (halo)alkylcarbonyloxy group refers to alkylcarbonyloxyoptionally substituted with halogen for one or more than one hydrogenatoms.

[0026] The term “C₁-C₁₀” or the like refers to the number of carbonatoms constituting the alkyl, alkenyl, or alkynyl group in eachsubstituent. For example, C₁-C₄ (halo)alkylcarbonyl means alkylcarbonyloptionally substituted with halogen for one or more hydrogen atomswherein the alkyl part is constituted by C₁-C₄ carbon atoms.

[0027] In compounds (X), each group includes specific ones as listedbelow:

[0028] The C₁-C₅ (halo)alkyl group represented by R¹ or R² may includemethyl, ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl,2,2-dimethylpropyl, chloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, 2,2,2-trifluoroethyl, and 1,1,2,2-tetrafluoroethyl.

[0029] The C₁-C₅ (halo)alkyloxy group represented by R¹ or R² mayinclude methoxy, ethoxy, 1-methylethoxy, trifluoromethoxy,difluoromethoxy, 2,2,2-trifluoroethoxy, and 1,1,2,2-tetrafluoroethoxy.

[0030] The C₂-C₅ (halo)alkenyl group represented by R¹ or R² may includevinyl, 1-propenyl, 2-propenyl, 2,2-difluorovinyl, and1,2,2-trifluorovinyl.

[0031] The C₂-C₅ (halo)alkynyl group represented by R¹ or R² may includeethynyl, 1-propynyl, 2-propynyl and 3,3,3-trifluoro-1-propynyl.

[0032] The C₁-C₁₀ alkyl group represented by R³ or R⁴ may includemethyl, ethyl, 1-methylethyl, propyl, 2-methylpropyl,2,2-dimethylpropyl, butyl, 3-methylbutyl, and 3,3-dimethylbutyl.

[0033] The C₂-C₁₀ alkenyl group represented by R³ or R⁴ may includevinyl, allyl, 1-propenyl, 3-butenyl, 2-methyl-1-propenyl,3-methyl-2-butenyl, 3-pentenyl, 4-pentenyl, 3-methyl-3-butenyl, and4-methyl-3-pentenyl.

[0034] The C₂-C₁₀ alkynyl group represented by R³ or R⁴ may includeethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-methyl-1-butynyl, and3,3-dimethyl-1-butynyl.

[0035] The C₂-C₆ (halo)alkylene group represented by R³ and R⁴ takentogether may include ethylene, propylene, trimethylene, tetramethylene,and 3,3-dimethyltrimethylene.

[0036] The C₄-C₆ (halo)alkenylene group represented by R³ and R⁴ takentogether may include 2-butenylene and 2-pentenylene.

[0037] The halogen atom represented by R⁵ or R⁶ may include fluorine,chlorine, bromine, and iodine.

[0038] The C₁-C₄ (halo)alkyl group represented by R⁵ or R⁶ may includemethyl, ethyl, propyl, 1-methylethyl, 1,1-dimethylethyl,trifluoromethyl, pentafluoroethyl, 3,3,3-trifluoroethyl, and1,1,2,2-tetrafluoroethyl.

[0039] The C₂-C₄ (halo)alkenyl group represented by R⁵ or R⁶ may includevinyl, 1-propenyl, 2-propenyl and 2,2-difluorovinyl.

[0040] The C₂-C₄ (halo)alkynyl group represented by R⁵ or R⁶ may includeethynyl, 1-propynyl, 2-propynyl and 3,3,3-trifluoro-1-propynyl.

[0041] The C₁-C₄ (halo)alkyloxy group represented by R⁵ or R⁶ mayinclude methoxy, ethoxy, propoxy, trifluoromethoxy,bromodifluoromethoxy, difluoromethoxy, chlorodifluoromethoxy,pentafluoroethoxy, 2,2,2-trifluoroethoxy, and 1,1,2,2-tetrafluoroethoxy.

[0042] The C₁-C₄ (halo)alkylthio group represented by R⁵ or R⁶ mayinclude methylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, and1,1,2,2-tetrafluoroethylthio.

[0043] The C₁-C₄ (halo)alkylsulfinyl group represented by R⁵ or R⁶ mayinclude methylsulfinyl and trifluoromethylsulfinyl.

[0044] The C₁-C₄ (halo)alkylsulfonyl group represented by R⁵ or R⁶ mayinclude methylsulfonyl and trifluoromethylsulfonyl.

[0045] The C₁-C₄ (halo)alkylcarbonyl group represented by R⁵ or R⁶ mayinclude acetyl, propionyl, and trifluoroacetyl.

[0046] The C₁-C₄ (halo)alkyloxycarbonyl group represented by R⁵ or R⁶may include methoxycarbonyl and 2,2,2-trifluoroethoxycarbonyl.

[0047] The C₁-C₄ (halo)alkylcarbonyloxy group represented by R⁵ or R⁶may include acetyloxy, propionyloxy, and trifluoroacetyloxy.

[0048] The phenyloxy optionally substituted with halogen or C₁-C₃ alkyl,which is represented by R⁵ or R⁶, may include phenoxy, p-methylphenoxy,m-methylphenoxy, and p-chlorophenoxy.

[0049] The phenylthio group optionally substituted with halogen or C₁-C₃alkyl, which is represented by R⁵ or R⁶, may include phenylthio,p-methylphenylthio, m-methylphenylthio, and p-chlorophenylthio.

[0050] The embodiments of compounds (X) may include the followingcompounds:

[0051] The malononitrile compounds of formula (X) wherein R¹ ishydrogen, and R² is C₁-C₅ (halo)alkyl, C₂-C₅ (halo)alkenyl, or hydrogen;

[0052] The malononitrile compounds of formula (X) wherein R¹ and R² areboth hydrogen;

[0053] The malononitrile compounds of formula (X) wherein R₃ is C₁-C₁₀alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, or hydrogen; R⁴ is C₁-C₁₀ alkyl,C₂-C₁₀ alkenyl, or C₂-C₁₀ alkynyl;

[0054] The malononitrile compounds of formula (X) wherein R³ is hydrogenand R⁴ is C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, or C₂-C₁₀ alkynyl;

[0055] The malononitrile compounds of formula (X) wherein R³ is hydrogenand R⁴ is C₁-C₁₀ alkyl or C₂-C₁₀ alkenyl;

[0056] The malononitrile compounds of formula (X) wherein R³ is hydrogenand R⁴ is C₁-C₁₀ alkyl;

[0057] The malononitrile compounds of formula (X) wherein R⁵ is halogen,n is an integer of 0 to 2;

[0058] The malononitrile compounds of formula (X) wherein R⁶ is halogen,cyano, nitro, C₁-C₄ haloalkyl, C₁-C₄ haloalkyloxy, or C₁-C₄haloalkylthio;

[0059] The malononitrile compounds of formula (X) wherein R⁵ is halogen,n is an integer of 0 to 2, and R⁶ is halogen, cyano, nitro, C₁-C₄(halo)alkyl, C₁-C₄ (halo)alkyloxy, or C₁-C₄ (halo)alkylthio;

[0060] The malononitrile compounds of formula (X) wherein R³ ishydrogen; R⁴ is C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, or C₂-C₁₀ alkynyl, R⁵ ishalogen, n is an integer of 0 to 2, and R⁶ is halogen, cyano, nitro,C₁-C₄ (halo)alkyl, C₁-C₄ (halo)alkyloxy, or C₁-C₄ (halo)alkylthio;

[0061] The malononitrile compounds of formula (X) wherein R¹ ishydrogen, R² is C₁-C₅ (halo)alkyl, C₂-C₅ (halo)alkenyl, or hydrogen, R³is hydrogen; R⁴ is C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, or C₂-C₁₀ alkynyl, R⁵is halogen, n is an integer of 0 to 2, and R⁶ is halogen, cyano, nitro,C₁-C₄ (halo)alkyl, C₁-C₄ (halo)alkyloxy, or C₁-C₄ (halo)alkylthio;

[0062] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is trifluoromethyl;

[0063] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is difluoromethoxy;

[0064] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is trifluoromethoxy;

[0065] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is trifluoromethylthio;

[0066] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is 1,1,2,2-tetrafluoroethoxy;

[0067] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is chlorine;

[0068] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is bromine;

[0069] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is fluorine;

[0070] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is cyano;

[0071] The malononitrile compounds of formula (X) wherein R⁴ is vinyland R⁶ is nitro;

[0072] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is trifluoromethyl;

[0073] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is difluoromethoxy;

[0074] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is trifluoromethoxy;

[0075] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is trifluoromethylthio;

[0076] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is 1,1,2,2-tetrafluoroethoxy;

[0077] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is chlorine;

[0078] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is bromine;

[0079] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is fluorine;

[0080] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is cyano;

[0081] The malononitrile compounds of formula (X) wherein R⁴ is allyland R⁶ is nitro;

[0082] The malononitrile compounds of formula (X) wherein R⁴ is ethyland R⁶ is trifluoromethyl;

[0083] The malononitrile compounds of formula (X) wherein R⁴ is ethyland R⁶ is trifluoromethoxy;

[0084] The malononitrile compounds of formula (X) wherein R⁴ is ethyland R⁶ is trifluoromethylthio;

[0085] The malononitrile compounds of formula (X) wherein R⁴ is ethyland R⁶ is chlorine;

[0086] The malononitrile compounds of formula (X) wherein R⁴ is ethyland R⁶ is cyano;

[0087] The malononitrile compounds of formula (X) wherein R⁴ is3-butenyl and R⁶ is trifluoromethyl;

[0088] The malononitrile compounds of formula (X) wherein R⁴ is3-butenyl and R⁶ is trifluoromethoxy;

[0089] The malononitrile compounds of formula (X) wherein R⁴ is3-butenyl and R⁶ is trifluoromethylthio;

[0090] The malononitrile compounds of formula (X) wherein R⁴ is3-butenyl and R⁶ is chlorine;

[0091] The malononitrile compounds of formula (X) wherein R⁴ is3-butenyl and R⁶ is cyano;

[0092] The malononitrile compounds of formula (X) wherein R⁴ is2-methyl-1-propenyl and R⁶ is trifluoromethyl;

[0093] The malononitrile compounds of formula (X) wherein R⁴ is2-methyl-1-propenyl and R⁶ is trifluoromethoxy;

[0094] The malononitrile compounds of formula (X) wherein R⁴ is2-methyl-1-propenyl and R⁶ is trifluoromethylthio;

[0095] The malononitrile compounds of formula (X) wherein R⁴ is2-methyl-1-propenyl and R⁶ is chlorine;

[0096] The malononitrile compounds of formula (X) wherein R⁴ is2-methyl-1-propenyl and R⁶ is cyano;

[0097] The malononitrile compounds of formula (X) wherein R⁴ is1-propenyl and R⁶ is trifluoromethyl;

[0098] The malononitrile compounds of formula (X) wherein R⁴ is1-propenyl and R⁶ is trifluoromethoxy;

[0099] The malononitrile compounds of formula (X) wherein R⁴ is1-propenyl and R⁶ is trifluoromethylthio;

[0100] The malononitrile compounds of formula (X) wherein R⁴ is1-propenyl and R⁶ is chlorine;

[0101] The malononitrile compounds of formula (X) wherein R⁴ is1-propenyl and R⁶ is cyano;

[0102] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is trifluoromethyl;

[0103] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is difluoromethoxy;

[0104] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is trifluoromethoxy;

[0105] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is trifluoromethylthio;

[0106] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is 1,1,2,2-tetrafluoroethoxy;

[0107] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is chlorine;

[0108] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is bromine;

[0109] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is fluorine;

[0110] The malononitrile compounds of formula (X) wherein R⁴ is2-methylpropyl and R⁶ is cyano;

[0111] The malononitrile compounds of formula (X) wherein R⁴ is−2-methylpropyl and R⁶ is nitro;

[0112] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is trifluoromethyl;

[0113] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is difluoromethoxy;

[0114] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is trifluoromethoxy;

[0115] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is trifluoromethylthio;

[0116] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is 1,1,2,2-tetrafluoroethoxy;

[0117] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is chlorine;

[0118] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is bromine;

[0119] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is fluorine;

[0120] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is cyano;

[0121] The malononitrile compounds of formula (X) wherein R⁴ is2,2-dimethylpropyl and R⁶ is nitro;

[0122] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is trifluoromethyl;

[0123] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is difluoromethoxy;

[0124] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is trifluoromethoxy;

[0125] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is trifluoromethylthio;

[0126] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is 1,1,2,2-tetrafluoroethoxy;

[0127] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is chlorine;

[0128] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is bromine;

[0129] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is fluorine;

[0130] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is cyano;

[0131] The malononitrile compounds of formula (X) wherein R⁴ is1-methylethyl and R⁶ is nitro.

[0132] The preferred compounds among compound (X) are the compoundswherein R⁶ is halogen, cyano, nitro, C₁-C₄ haloalkyl, C₁-C₄ haloalkyloxyor C₁-C₄ haloalkylthio; the compounds wherein R³ and R⁴ are the same ordifferent and independently C₁-C₅ alkyl, C₂-C₅ alkenyl, C₂-C₅ alkynyl,or hydrogen, or R³ and R⁴ are taken together to form C₂-C₆(halo)alkylene; or the compounds wherein n is 1 to 3 and at least one ofR⁵ is halogen, cyano, nitro, C₁-C₄ haloalkyl, C₁-C₄ haloalkyloxy orC₁-C₄ (halo)alkylthio. More preferred compounds are the compoundswherein R⁶ is halogen, cyano, nitro, C₁-C₄ fluoroalkyl, C₁-C₄fluoroalkyloxy or C₁-C₄ fluoroalkylthio; or the compounds wherein n is 1to 3 and at least one of R⁵ is halogen, cyano, nitro, C₁-C₄ fluoroalkyl,C₁-C₄ fluoroalkyloxy or C₁-C₄ fluoroalkylthio.

[0133] The following will describe the production processes forcompounds (X).

[0134] The compounds (X) can be produced by, for example, the following(Production Process 1) to (Production Process 5).

[0135] (Production Process 1)

[0136] This is a process by reacting compound (a) with compound (b) inthe presence of a base.

[0137] wherein R¹, R², R³, R⁴, R⁵, R⁶, and n are as defined above, and Zis halogen, methanesulfonyl, trifluoromethanesulfonyl, ortoluenesulfonyl.

[0138] The reaction is usually carried out in a solvent. The solventwhich can be used in the reaction may include acid amides such asdimethylformamide; ethers such as diethyl ether and tetrahydrofuran;organic sulfur compounds such as dimethylsulfoxide and sulfolane;halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene;aromatic hydrocarbons such as toluene and xylene; water; and mixturesthereof. The base which can be used in the reaction may includeinorganic bases such as sodium hydride, sodium hydroxide, potassiumhydroxide, and potassium carbonate; alkali metal alkoxides such assodium methoxide, sodium ethoxide, and potassium tert-butoxide; alkalimetal amides such as lithium diisopropylamide; and organic bases such as4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, and1,8-diazabicylco[5.4.0]-7-undecene. The amount of base used in thereaction is usually in a ratio of 1 to 10 moles relative to 1 mole ofcompound (a).

[0139] The reaction temperature is usually in the range of −20° C. to100° C.

[0140] The reaction time is usually in the range of 1 to 24 hours.

[0141] The amount of compound (b) used in the reaction is usually in aratio of 1 to 10 moles relative to 1 mole of compound (a).

[0142] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredcompounds, which may be purified by a technique such as chromatographyor recrystallization.

[0143] (Production Process 2)

[0144] This is a process by reacting compound (c) with compound (d) inthe presence of a base.

[0145] wherein R¹, R², R⁸, R⁴, R⁵, R⁶, n, and Z are as defined above.

[0146] The reaction is usually carried out in a solvent. The solventwhich can be used in the reaction may include acid amides such asdimethylformamide; ethers such as diethyl ether and tetrahydrofuran;organic sulfur compounds such as dimethylsulfoxide and sulfolane;halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene;aromatic hydrocarbons such as toluene and xylene; water; and mixturesthereof.

[0147] The base which can be used in the reaction may include inorganicbases such as sodium hydride, sodium hydroxide, potassium hydroxide, andpotassium carbonate; alkali metal alkoxides such as sodium methoxide,sodium ethoxide, and potassium tert-butoxide; alkali metal amides suchas lithium diisopropylamide; and organic bases such as4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, and1,8-diazabicylco[5.4.0]-7-undecene. The amount of base used in thereaction is usually in a ratio of 1 to 10 moles relative to 1 mole ofcompound (a).

[0148] The reaction temperature is usually in the range of −20° C. to100° C.

[0149] The reaction time is usually in the range of 1 to 24 hours.

[0150] The amount of compound (b) used in the reaction is usually in aratio of 1 to 10 moles relative to 1 mole of compound (a).

[0151] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredcompounds, which may be purified by a technique such as chromatographyor recrystallization.

[0152] The compound (a) can be produced through a route, for example, asshown in the following scheme.

[0153] wherein R¹, R², R⁵, R⁶, and n are as defined above.

[0154] (Step 1)

[0155] The compound (f) can be produced by reacting compound (e) withmalononitrile.

[0156] The reaction is usually carried out in a solvent and in thepresence of a base. The solvent which can be used in the reaction mayinclude acid amides such as N,N-dimethylformamide; ethers such asdiethyl ether and tetrahydrofuran; halogenated hydrocarbons such aschloroform, 1,2-dichloroethane, and chlorobenzene; aromatic hydrocarbonssuch as toluene and xylene; alcohols such as methanol, ethanol, andisopropanol; and mixtures thereof.

[0157] The base which can be used in the reaction may includetetrabutylammonium hydroxide. The amount of base used in the reaction isusually in a ratio of 0.01 to 0.5 mole relative to 1 mole of compound(e).

[0158] The amount of malononitrile used in the reaction is usually in aratio of 1 to 10 moles relative to 1 mole of compound (e).

[0159] The reaction temperature is usually in the range of −20° C. to200° C.

[0160] The reaction time is usually in the range of 1 to 24 hours.

[0161] The reaction may be carried out, while removing, if necessary,water which is generated by the reaction, from the reaction system.

[0162] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredcompounds, which may be purified by a technique such as chromatographyor recrystallization.

[0163] (Step 2)

[0164] (1) The case where R² is a substituent other than hydrogen andcyano:

[0165] The compound (a) can be produced by reacting compound (f) with anorganometallic compound.

[0166] The reaction is usually carried out in a solvent and, ifnecessary, in the presence of a copper salt.

[0167] The solvent which can be used in the reaction may include etherssuch as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such astoluene and xylene; and mixtures thereof.

[0168] The organometallic compound which can be used in the reaction mayinclude organic magnesium compounds such as methyl magnesium iodide,ethyl magnesium bromide, isopropyl magnesium bromide, vinyl magnesiumbromide, ethynyl magnesium bromide, and dimethyl magnesium; organiclithium compounds such as methyl lithium; organic zinc compounds such asdiethyl zinc; and organic copper compounds such as trifluoromethylcopper. The amount of organometallic compound used in the reaction isusually in a ratio of 1 to 10 moles relative to 1 mole of compound (f).

[0169] The copper salt which can be used in the reaction may includecopper (I) iodide and copper (I) bromide. The amount of copper salt usedin the reaction is usually not greater than 1 mole relative to 1 mole ofcompound (f).

[0170] The reaction temperature is usually in the range of −20° C. to100° C.

[0171] The reaction time is usually in the range of 1 to 24 hours.

[0172] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredcompounds, which may be purified by a technique such as chromatographyor recrystallization.

[0173] (2) The case where R² is hydrogen:

[0174] The compound (a) can be produced by subjecting compound (f) toreduction.

[0175] The reduction is usually carried out in a solvent.

[0176] The solvent which can be used in the reaction may include etherssuch as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such astoluene and xylene; alcohols such as methanol, ethanol, and propanol;water; and mixtures thereof.

[0177] The reducing agent which can be used in the reaction may includesodium borohydride. The amount of reducing agent used in the reaction isusually in a ratio of 0.25 to 2 moles relative to 1 mole of compound(f).

[0178] The reaction time is usually in the range of a moment to 24hours.

[0179] The reaction temperature is usually in the range of 0° C. to 50°C.

[0180] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredcompounds, which may be purified by a technique such as chromatographyor recrystallization.

[0181] (3) The case where R² is cyano:

[0182] The compound (a) can be produced by reacting compound (f) with acyanide.

[0183] The solvent which can be used in the reaction may include etherssuch as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such astoluene and xylene; and mixtures thereof.

[0184] The cyanide which can be used in the reaction may includetetrabutylammonium cyanide. The amount of cyanide used in the reactionis usually in a ratio of 1 to 10 moles relative to 1 mole of compound(f).

[0185] The reaction temperature is usually in the range of −20° C. to100° C.

[0186] The reaction time is usually in the range of 1 to 24 hours.

[0187] After the reaction, the reaction mixture is poured into water,followed by ordinary post-treatment procedures including extraction withan organic solvent and concentration, thereby isolating the desiredcompounds, which may be purified by a technique such as chromatographyor recrystallization.

[0188] (Production Process 3)

[0189] The compounds wherein R¹ is C₁-C₅ (halo)alkyl, R² and R³ are bothhydrogen, and R⁴ is CH₂═CH can also be produced by the process as shownin the following scheme.

[0190] wherein R⁵, R⁶, and n are as defined above, R¹¹ is C₁-C₅(halo)alkyl, Bu is butyl, and AIBN is azobisisobutyronitrile.

[0191] The reaction can be carried out according to the process asdescribed in J. Am. Chem. Soc., 110, 1289 (1988).

[0192] (Production Process 4)

[0193] The compounds wherein R¹ is cyano, R² and R³ are both hydrogen,R⁴ is CH₂═CH can also be produced by the process as shown in thefollowing scheme.

[0194] wherein R⁵, R⁶, and n are as defined above, dba isdibenzylideneacetone, and dppf is 1,1′-bis(diphenylphosphino)ferrocene.

[0195] The reaction can be carried out according to the conditions asdescribed in Tetrahedron Lett., 41, 2911 (2000).

[0196] (Production Process 5)

[0197] The compounds wherein R¹ is C₁-C₅ (halo)alkyloxy, R² and R³ areboth hydrogen, and R⁴ is CH₂═CH can also be produced by the process asshown in the following scheme.

[0198] wherein R⁵, R⁶, and n are as defined above, R¹² is C₁-C₅(halo)alkyloxy, Ph is phenyl, and THF is tetrahydrofuran.

[0199] The reaction can be carried out according to the conditions asdescribed in J. Am. Chem. Soc., 120, 6838 (1998).

[0200] The pests against which compounds (X) exhibit controllingactivity may include insect pests, acarine pests, and nematode pests,specific examples which are as follows:

[0201] Hemiptera:

[0202] Delphacidae such as Laodelphax striatellus, Nilaparvata lugens,and Sogatella furcifera;

[0203] Deltocephalidae such as Nephotettix cincticeps and Nephotettixvirescens;

[0204] Aphididae such as Aphis gossypii and Myzus persicae;

[0205] Pentatomidae such as Nezara antennata, Riptortus clavetusEysarcoris lewisi, Eysarcoris parvus, Plautia stali and Halyomorphamisia;

[0206] Aleyrodidae such as Trialeurodes vaporariorum and Bemisiaargentifolii;

[0207] Coccidae such as Aonidiella aurantii, Comstockaspis perniciosa,Unaspis citri, Ceroplastes rubens, and Icerya purchasi;

[0208] Tingidae;

[0209] Psyllidae;

[0210] Lepidoptera:

[0211] Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis,Notarcha derogata, and Plodia interpunctella;

[0212] Noctuidae such as Spodoptera litura, Pseudaletia separata,Thoricopiusia spp., Heliothis spp., and Helicoverpa spp.;

[0213] Pieridae such as Pieris rapae;

[0214] Tortricidae such as Adoxophyes spp., Grapholita molesta, andCydia pomonella;

[0215] Carposinidae such as Carposina niponensis;

[0216] Lyonetiidae such as Lyonetia spp.;

[0217] Lymantriidae such as Lyamantria spp. and Euproctis spp.;

[0218] Yponomentidae such as Plutella xylostella;

[0219] Gelechiidae such as Pectinophora gossypiella;

[0220] Arctiidae such as Hyphantria cunea;

[0221] Tineidae such as Tinea translucens and Tineola bisselliella;

[0222] Diptera:

[0223] Calicidae such as Culex pipiens pallens, Culex tritaeniorhynchus,and Culex quinquefasciatus;

[0224] Aedes spp. such as Aedes aegypti and Aedes albopictus;

[0225] Anopheles spp. such as Anopheles sinensis;

[0226] Chironomidae;

[0227] Muscidae such as Musca domestica and Muscina stabulans;

[0228] Calliphoridae;

[0229] Sarcophagidae;

[0230] Fanniidae;

[0231] Anthomyiidae such as Delia platura and Delia antiqua;

[0232] Tephritidae;

[0233] Drosophilidae;

[0234] Psychodidae;

[0235] Simuliidae;

[0236] Tabanidae;

[0237] Stomoxyidae;

[0238] Agromyzidae;

[0239] Coleoptera:

[0240] Diabrotica spp. such as Diabrotica virgifera and Diabroticaundecimpunctata howardi;

[0241] Scarabaeidae such as Anomala cuprea and Anomala rufocuprea;

[0242] Curculionidae such as Sitophilus zeamais, Lissorhoptrusoryzophilus, and Callosobruchuys chienensis;

[0243] Tenebrionidae such as Tenebrio molitor and Trbolium castaneum;

[0244] Chrysomelidae such as Oulema oryzae, Aulacophora femoralis,Phyllotreta striolata, and Leptinotarsa decemlineata;

[0245] Anobiidae;

[0246] Epilachna spp. such as Epilachna vigintioctopunctata;

[0247] Lyctidae;

[0248] Bostrychidae;

[0249] Cerambycidae;

[0250] Paederus fuscipes;

[0251] Dictyoptera:

[0252]Blattella germanica, Periplaneta fuliginosa, Periplanetaamericana, Periplaneta brunnea, and Blatta orientalis;

[0253] Thysanoptera:

[0254]Thrips palmi, Thrips tabaci, Frankliniella occidentalis,Frankliniella intonsa;

[0255] Hymenoptera:

[0256] Formicidae;

[0257] Vespidae;

[0258] Bethylidae;

[0259] Tenthredinidae such as Athalia japonica;

[0260] Orthoptera:

[0261] Gryllotalpidae;

[0262] Acrididae;

[0263] Siphonaptera:

[0264]Ctenocephalides felis, Ctenocephalides canis, Pulex irritans,Xenopsylla cheopis;

[0265] Anoplura:

[0266]Pediculus humanus corporis, Phthirus pubis, Haematopinuseurysternus, and Dalmalinia ovis;

[0267] Isoptera:

[0268] Reticulitermes speratus and Coptotermes formosanus;

[0269] Acarina:

[0270] Tetranychidae such as Tetranychus urticae, Tetranychus kanzawai,Panonychus citri, Panonychus ulmi, and Oligonychus spp.;

[0271] Eriophyidae such as Aculops pelekassi and Aculus schlechtendali;

[0272] Tarsonemidae such as Polyphagotarsonem us latus;

[0273] Tenuipalpidae;

[0274] Tuckerellidae;

[0275] Ixodidae such as Haemaphysalis longicornis, Haemaphysalis flava,Dermacentor taiwanicus, Ixodes ovatus, Ixodes persulcatus, and Boophilusmicroplus;

[0276] Acaridae such as Tophagus putrescentiae;

[0277] Epidermoptidae such as Dermatophagoides farinae andDermatophagoides ptrenyssn us;

[0278] Cheyletidae such as Cheyletus eruditus, Cheyletus malaccensis,and Cheyletus moorei;

[0279] Dermanyssidae;

[0280] Arachnida:

[0281] Chiracanthium japonicum and Latrodectus hasseltii;

[0282] Chilopoda:

[0283] Thereuonema hilgendorfliand Scolopendra suhspinipes;

[0284] Diplopoda:

[0285] Oxidus gracilis and Nedyopus tambanus;

[0286] Isopoda:

[0287] Armadillidium vulgare;

[0288] Gastropoda:

[0289] Limax marginatus and Limax flavus;

[0290] Nematoda:

[0291] Pratylenchus coffeae, Pratylenchus fallax, Heterodera glycines,Globodera rostochiensis, Meloidogyne hapla, and Meloidogyne incognita.

[0292] When compounds (X) are used as the active ingredients ofpesticide compositions, they may be used as such without addition of anyother ingredients. However, they are usually used in admixture withsolid carriers, liquid carriers and/or gaseous carriers, and ifnecessary, by addition of adjuvants such as surfactants, followed byformulation into various forms such emulsifiable concentrates, oilformulations, flowables, dusts, wettable powders, granules, pasteformulations, microcapsule formulations, foams, aerosol formulations,carbon dioxide gas formulations, tablets, or resin formulations. Theseformulations may be used by processing into poison baits, shampoo,mosquito coils, electric mosquito mats, smokes, fumigants, or sheets.

[0293] In these formulations, compounds (X) are usually contained eachin an amount of 0.1% to 95% by weight.

[0294] The solid carrier which can be used in the formulation mayinclude the following materials in fine powder or granular form: clays(e.g., kaolin clay, diatomaceous earth, bentonite, Fubasami clay, acidclay); talc, ceramic, and other inorganic minerals (e.g., sericite,quartz, sulfur, activated carbon, calcium carbonate, hydrated silica);and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate,ammonium nitrate, ammonium chloride, urea).

[0295] The liquid carrier may include aromatic or aliphatic hydrocarbons(e.g., xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosine,light oils, hexane, cyclohexane); halogenated hydrocarbons (e.g.,chlorobenzene, dichloromethane, dichloroethane, trichloroethane);alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol, hexanol,ethylene glycol); ethers (e.g., diethyl ether, ethylene glycol dimethylether, diethylene glycol monomethyl ether, diethylene glycol monoethylether, propylene glycol monomethyl ether, tetrahydrofuran, dioxane);esters (e.g., ethyl acetate, butyl acetate); ketones (e.g., acetone,methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone); nitriles(acetonitrile, isobutyronitrile); sulfoxides (e.g., dimethylsulfoxide);acid amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide);vegetable oils (e.g., soy bean oil and cotton seed oil); plant essentialoils (e.g., orange oil, hyssop oil, lemon oil); and water.

[0296] The gaseous carrier may include butane gas, Freon gas, liquefiedpetroleum gas (LPG), dimethyl ether, and carbon dioxide.

[0297] The surfactant may include alkyl sulfate salts; alkylsulfonicacid salts; alkylarylsulfonic acid salts; alkyl aryl ethers and theirpolyoxyethylene derivatives; polyethylene glycol ethers; polyol esters;and sugar alcohol derivatives.

[0298] The other adjuvants may include binders, dispersants, andstabilizers, specific examples of which are casein, gelatin,polysaccharides (e.g., starch, gum arabic, cellulose derivatives,alginic acid), lignin derivatives, bentonite, sugars, syntheticwater-soluble polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone,polyacrylic acid), PAP (isopropyl acid phosphate), BHT(2,6-di-t-butyl-4-methylphenol), BHA (mixtures of2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol), vegetableoils, mineral oils, fatty acids, and fatty acid esters.

[0299] The base material for resin formulations may include vinylchloride polymers and polyurethanes. These base materials may contain,if necessary, plasticizers such as phthalic acid esters (e.g., dimethylphthalate, dioctyl phthalate), adipic acid esters, and stearic acid. Theresin formulations can be obtained by kneading the compounds into thebase materials with an ordinary kneader and subsequent forming such asinjection molding, extrusion, or pressing. They can be processed, ifnecessary, though further forming and cutting into resin formulations invarious shapes such as plates, films, tapes, nets, or strings. Theseresin formulations are processed as, for example, collars for animals,ear tags for animals, sheet formulations, attractive strings, or polesfor horticultural use.

[0300] The base material for poison baits may include grain powders,vegetable oils, sugars, and crystalline cellulose. If necessary,additional agents may be added, including antioxidants such asdibutylhydroxytoluene and nordihydroguaiaretic acid; preservatives suchas dehydroacetic acid; agents for preventing children and pets fromerroneously eating, such as hot pepper powder; and pest-attractiveflavors such as cheese flavor, onion flavor, and peanut oil.

[0301] The pesticide compositions of the present invention may be usedby, for example, direct application to pests and/or application to thehabitats of pests (e.g., plant bodies, animal bodies, soil).

[0302] When the pesticide compositions of the present invention are usedfor the control of pests in agriculture and forestry, their applicationamounts are usually 1 to 10,000 g/ha, preferably 10 to 500 g/ha.Formulations such as emulsifiable concentrates, wettable powders,flowables, and microcapsule formulations are usually used after dilutionwith water to have an active ingredient concentration of 1 to 1000 ppm,while formulations such as dusts and granules are usually used as such.These formulations may be directly applied to plants to be protectedfrom pests. These formulations can also be incorporated into soil forthe control of pests inhabiting the soil, or can also be applied to bedsbefore planting or applied to planting holes or plant bottoms in theplanting. Further, the pesticide compositions of the present inventionin the form of sheet formulations can be applied by the methods in whichthe sheet formulations are wound around plants, disposed in the vicinityof plants, or laid on the soil surface at the plant bottoms.

[0303] When the pesticide compositions of the present invention are usedfor the prevention of epidemics, their application amounts as activeingredient amounts are usually 0.001 to 10 mg/m³ for spatial applicationor 0.001 to 100 mg/m² for planar application. Formulations such asemulsifiable concentrates, wettable powders, and flowables are usuallyapplied after dilution with water to have an active ingredientconcentration of 0.01 to 10,000 ppm, while formulations such as oilformulations, aerosols, smokes, or poison baits are usually applied assuch.

[0304] When the pesticide compositions of the present invention are usedfor the control of external parasites on domestic animals such ascattle, sheep, goat, and fowl or small animals such as dogs, cats, rats,and mice, they can be used by the veterinarily well-known methods. Asthe specific methods of use, administration is achieved by, for example,tablets, feed incorporation, suppositories, or injections (e.g.,intramuscular, subcutaneous, intravenous, intraperitoneal) for systemiccontrol, or by, for example, spraying, pour-on treatment, or spot-ontreatment with an oil formulation or an aqueous solution, washinganimals with a shampoo formulation, or attachment of a collar or ear tagprepared from a resin formulation to animals for non-systemic control.The amounts of compounds (X) when administered to animal bodies areusually in the range of 0.1 to 1000 mg per 1 kg weight of each animal.

[0305] The pesticide compositions of the present invention can also beused in admixture or combination with other insecticides, nematocides,acaricides, bactericides, fungicides, herbicides, plant growthregulators, synergists, fertilizers, soil conditioners, animal feeds,and the like.

[0306] Examples of the insecticides and acaricides includeorganophosphorus compounds such as fenitrothion[O,O-dimethylO-(3-methyl-4-nitrophenyl) phosphorothioate], fenthion[O,O-dimethylO-(3-methyl-4-(methythio)phenyl) phosphorothioate], diazinon[O,O-diethylO-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate],chlorpyrifos[O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate],DDVP[2,2-dichlorovinyl dimethyl phosphate], cyanophos[O-4-cyanophenylO,O-dimethyl phosphorothioate], dimethoate[O,O-dimethylS-(N-methylcarbamoylmethyl)dithiophosphate], phenthoate[ethyl2-dimethoxyphosphinothioylthio(phenyl)acetate],malathion[diethyl(dimethoxyphosphinothioylthio)succinate], andazinphosmethyl[S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethylO,O-dimethyl phosphorodithioate]; carbamate compounds such as BPMC(2-sec-butyl-phenyl methylcarbamate), benfracarb[ethylN-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-isopropyl-p-alaninate],propoxur[2-isopropoxyphenyl N-methylcarbamate] and carbaryl[1-naphthylN-methylcarbamate]; pyrethroid compounds such asetofenprox[2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether],fenvalerate[(RS)-α-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methyl-butyrate],esfenvalerate[(S)-α-cyano-3-phenoxybenzyl(S)-2-(4-chlorophenyl)-3-methylbutyrate],fenpropathrin[(RS)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate],cypermethrin[(RS)-α-cyano-3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],permethrin[3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],cyhalothrin[(RS)-α-cyano-3-phenoxybenzyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],deltamethrin[(S)-α-cyano-3-phenoxybenzyl(1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-carboxylate],cycloprothrin[(RS)-α-cyano-3-phenoxybenzyl(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate],fluvalinate[α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate],bifenthrin[2-methylbiphenyl-3-ylmethyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],2-methyl-2-(4-bromodifluoro-methoxyphenyl)propyl 3-phenoxybenzyl ether,tralomethrin[(S)-α-cyano-3-phenoxybenzyl(1R-cis)-3-{(1RS)(1,2,2,2-tetrabromoethyl)}-2,2-dimethyl-cyclopropanecarboxylate],silafluofen[(4-ethoxyphenyl){3-(4-fluoro-3-phenoxyphenyl)propyl}-dimethylsilane],d-phenothrin[3-phenoxybenzyl(1R-cis,trans)-chrysanthemate],cyphenothrin[(RS)-α-cyano-3-phenoxybenzyl(1R-cis,trans)-chrysanthemate],d-resmethrin[5-benzyl-3-furylmethyl(1R-cis,trans)-chrysanthemate],acrinathrin[(S)-α-cyano-3-phenoxybenzyl(1R,cis(Z))-2,2-dimethyl-3-{3-oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl}cyclopropanecarboxylate],cyfluthrin[(RS)-α-cyano-4-fluoro-3-phenoxybenzyl3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],tefluthrin[2,3,5,6-tetrafluoro-4-methylbenzyl(RS-cis(Z))-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],transfluthrin[2,3,5,6-tetrafluorobenzyl(1R-trans)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],tetramethrin[3,4,5,6-tetrahydrophthalimidomethyl(1RS)-cis,trans-chrysanthemate],allethrin[(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl(1RS)cis,trans-chrysanthemate],prallethrin[(S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl(1R)-cis,trans-chrysanthemate],empenthrin[(RS)-1-ethynyl-2-methyl-2-pentenyl(1R)-cis,trans-chrysanthemate],imiprothrin[2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl(1R)-cis,trans-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate],d-furamethrin[5-(2-propynyl) furfuryl(1R)-cis,trans-chrysanthemate] and5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate;neonicotinoid derivatives such asN-cyano-N′-methyl-N′-(6-chloro-3-pyridylmethyl)acetamidine;nitenpyram[N-(6-chloro-3-pyridylmethyl)-N-ethyl-N′-methyl-2-nitrovynylidenediamine];thiacloprid[1-(2-chloro-5-pyridylmethyl)-2-cyanoiminothiazoline];thiamethoxam[3-((2-chloro-5-thiazolyl)methyl)-5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine],1-methyl-2-nitro-3-((3-tetrahydrofuryl)methyl)guanidine and1-(2-chloro-5-thiazolyl)methyl-3-methyl-2-nitroguanidine;nitroiminohexahydro-1,3,5-triazine derivatives; chlorinated hydrocarbonssuch asendosulfan[6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepineoxide], γ-BHC [1,2,3,4,5,6-hexachlorocyclohexane] and1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylureacompounds such aschlorfluazuron[1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyn-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea],teflubenzuron[1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea]andflufenoxuron[1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea];juvenile hormone like compounds such as pyriproxyfen[4-phenoxyphenyl2-(2-pyridyloxy)propyl ether], methoprene[isopropyl(2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate] andhydroprene[ethyl(2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate];thiourea derivatives such asdiafenthiuron[N-(2,6-diisopropyl-4-phenoxyphenyl)-N′-tert-butylcarbodiimide];phenylpyrazole compounds;4-bromo-2-(4-chlorophenyl)-1-ethoxymethyl-5-trifluoromethylpyrrol-3-carbonitrile[chlorfenapil];metoxadiazone[5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2(3H)-one],bromopropylate[isopropyl 4,4′-dibromobenzilate],tetradifon[4-chlorophenyl 2,4,5-trichlorophenyl sulfone],chinomethionat[S,S-6-methylquinoxaline-2,3-diyldithiocarbonate],pyridaben[2-tert-butyl-5-(4-tertbutylbenzylthio)-4-chloropyridazin-3(2H)-one],fenpyroximate [tert-butyl(E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate],tebufenpyrad[N-(4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide],polynactins complex[tetranactin, dinactin and trinactin], pyrimidifen[5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrimidin-4-amine],milbemectin, abamectin, ivermectin and azadirachtin[AZAD]. Examples ofthe synergists include bis-(2,3,3,3-tetrachloropropyl)ether (S-421),N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MGK-264) andα-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene(piperonylbutoxide).

[0307] The present invention will further be illustrated by thefollowing production examples, formulation examples, and test examples;however, the present invention is not limited only to these examples. Inthe formulation examples, the compound numbers are those shown in Table1 below.

[0308] The following will describe some production examples forcompounds (X).

PRODUCTION EXAMPLE 1

[0309] First, 0.20 g of (4-chlorobenzyl)malononitrile was dissolved in 5ml of N,N-dimethylformamide, to which 46 mg of sodium hydride (60% inoil) was added, while stirring under ice cooling. After the evolution ofhydrogen gas ceased, while stirring under ice cooling, 0.44 ml of allylbromide was added dropwise, followed by further stirring at roomtemperature overnight. Then, 10% hydrochloric acid was added to thereaction mixture, which was extracted with diethyl ether. The organiclayer was successively washed with 10% hydrochloric acid, a saturatedaqueous sodium chloride solution, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to give 0.13 g of2-allyl-2-(4-chlorobenzyl)malononitrile (compound 1).

[0310] Yield: 54%;

[0311] n_(D) ^(22.0): 1.5326.

PRODUCTION EXAMPLE 2

[0312] Using 0.60 g of (1-(4-chlorophenyl)-1-methylethyl)malononitrile,10 ml of N,N-dimethylformamide, 121 mg of sodium hydride (60% in oil),and 1.20 ml of allyl bromide, and according to the process described inthe Production Example 1, there was obtained 0.60 g of2-allyl-2-(1-(4-chlorophenyl)-1-methylethyl)malononitrile (compound 2).

[0313] Yield: 85%;

[0314] n_(D) ^(23.5): 1.5354.

PRODUCTION EXAMPLE 3

[0315] Using 0.36 g of (1-(4-chlorophenyl)-2-methylpropyl)malononitrile,5 ml of N,N-dimethylformamide, 75 mg of sodium hydride (60% in oil), and0.20 ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.29 g of2-allyl-2-(1-(4-chlorophenyl)-2-methylpropyl)malononitrile (compound 3).

[0316] Yield: 69%;

[0317] n_(D) ^(22.5): 1.5272.

PRODUCTION EXAMPLE 4

[0318] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 126 mg of sodium hydride (60% in oil), and 0.40ml of 4-bromo-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.46 g of2-(3-butenyl)-2-(4-chlorobenzyl)malononitrile (compound 4).

[0319] Yield: 72%;

[0320] m.p.: 63.7° C.

PRODUCTION EXAMPLE 5

[0321] Using 1.12 g of (4-(trifluoromethyl)benzyl)malononitrile, 10 mlof N,N-dimethylformamide, 0.24 g of sodium hydride (60% in oil), and0.63 ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.58 g of2-allyl-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 5).

[0322] Yield: 44%;

[0323] m.p.: 80.2° C.

PRODUCTION EXAMPLE 6

[0324] Using 0.50 g of (4-cyanobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 132 mg of sodium hydride (60% in oil), and 0.42ml of 4-bromo-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.19 g of2-(3-butenyl)-2-(4-cyanobenzyl)malononitrile (compound 6).

[0325] Yield: 29%;

[0326] m.p.: 109.4° C.

PRODUCTION EXAMPLE 7

[0327] Using 0.50 g of (4-cyanobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 132 mg of sodium hydride (60% in oil), and 0.49ml of 5-bromo-1-pentene, and according to the process described in theProduction Example 1, there was obtained 0.12 g of2-(4-cyanobenzyl)-2-(4-pentenyl)malononitrile (compound 7).

[0328] Yield: 17%;

[0329] m.p.: 91.5° C.

PRODUCTION EXAMPLE 8

[0330] Using 0.20 g of (2-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 46 mg of sodium hydride (60% in oil), and 0.44 mlof allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.18 g of2-allyl-2-(2-chlorobenzyl)malononitrile (compound 8).

[0331] Yield: 74%;

[0332] n_(D) ^(20.5): 1.5329.

PRODUCTION EXAMPLE 9

[0333] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 160 mg of sodium hydride (60% in oil), and 0.68ml of cyclohexyl iodide, and according to the process described in theProduction Example 1, there was obtained 0.20 g of2-(4-chlorobenzyl)-2-cyclohexylmalononitrile (compound 9).

[0334] Yield: 28%;

[0335] m.p.: 107.9° C.

PRODUCTION EXAMPLE 10

[0336] Using 0.56 g of (1-(4-chlorophenyl)ethyl)malononitrile, 5 ml ofN,N-dimethylformamide, 160 mg of sodium hydride (60% in oil), and 0.56ml of 4-bromo-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.23 g of2-(3-butenyl)-2-(1-(4-chlorophenyl)ethyl)malononitrile (compound 10).

[0337] Yield: 32%;

[0338] n_(D) ^(25.5): 1.5259.

PRODUCTION EXAMPLE 11

[0339] Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 5 mlof N,N-dimethylformamide, 123 mg of sodium hydride, and 0.35 ml of allybromide, and according to the process described in the ProductionExample 1, there was obtained 0.26 g of2-allyl-2-(4-(trifluoromethoxy)benzyl)malononitrile (compound 11).

[0340] Yield: 45%;

[0341] n_(D) ^(24.5): 1.4682.

PRODUCTION EXAMPLE 12

[0342] Using 0.77 g of(1-(4-(trifluoromethoxy)phenyl-2-methylpropyl)malononitrile, 5 ml ofN,N-dimethylformamide, 160 mg of sodium hydride (60% in oil), and 0.55ml of 4-bromo-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.30 g of2-(3-butenyl)-2-(1-(4-(trifluoromethoxyphenyl)-2-methylpropyl)malononitrile(compound 12).

[0343] Yield: 33%;

[0344] n_(D) ^(25.5): 1.4686.

PRODUCTION EXAMPLE 13

[0345] Using 2.35 g of (4-bromobenzyl)malononitrile, 50 ml ofN,N-dimethylformamide, 0.44 g of sodium hydride (60% in oil), and 4.23ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 2.33 g of2-allyl-2-(4-bromobenzyl)malononitrile (compound 13).

[0346] Yield: 85%;

[0347] m.p.: 61.7° C.

PRODUCTION EXAMPLE 14

[0348] Using 1.81 g of (4-cyanobenzyl)malononitrile, 50 ml ofN,N-dimethylformamide, 0.44 g of sodium hydride (60% in oil), and 4.23ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 1.04 g of2-allyl-2-(4-cyanobenzyl)malononitrile (compound 14).

[0349] Yield: 47%;

[0350] m.p.: 81.9° C.

PRODUCTION EXAMPLE 15

[0351] Using 0.23 g of (4-(trifluoromethoxy)benzyl)malononitrile, 5 mlof N,N-dimethylformamide, 60 mg of sodium hydride (60% in oil), and 0.20ml of 4-bromo-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.16 g of2-(3-butenyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile (compound 15).

[0352] Yield: 54%;

[0353] n_(D) ^(25.5): 1.4657.

PRODUCTION EXAMPLE 16

[0354] Using 0.76 g of(1-(4-(trifluoromethoxy)phenyl)ethyl)malononitrile, 5 ml ofN,N-dimethylformamide, 180 mg of sodium hydride (60% in oil), and 0.61ml of 4-bromo-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.36 g of2-(3-butenyl)-2-(1-(4-(trifluoromethoxy)phenyl)ethyl)malononitrile(compound 16).

[0355] Yield: 39%;

[0356] n_(D) ^(25.5): 1.4673.

PRODUCTION EXAMPLE 17

[0357] Using 0.20 g of (3-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 46 mg of sodium hydride (60% in oil), and 0.44 mlof allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.11 g of2-allyl-2-(3-chlorobenzyl)malononitrile (compound 17).

[0358] Yield: 45%;

[0359] n_(D) ^(21.5): 1.5302.

PRODUCTION EXAMPLE 18

[0360] Using 1.74 g of (4-fluorobenzyl)malononitrile, 50 ml ofN,N-dimethylformamide, 0.44 g of sodium hydride (60% in oil), and 4.23ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 2.00 g of2-allyl-2-(4-fluorobenzyl)malononitrile (compound 18).

[0361] Yield: 93%;

[0362] n_(D) ^(24.5): 1.5028.

PRODUCTION EXAMPLE 19

[0363] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.33ml of isobutyl iodide, and according to the process described in theProduction Example 1, there was obtained 0.42 g of2-(4-chlorobenzyl)-2-isobutylmalononitrile (compound 19).

[0364] Yield: 65%;

[0365] m.p.: 73.2° C.

PRODUCTION EXAMPLE 20

[0366] Using 0.50 g of (2-methoxybenzyl)malononitrile, 10 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 1.1 mlof allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.50 g of2-allyl-2-(2-methoxybenzyl)malononitrile (compound 20).

[0367] Yield: 83%;

[0368] n_(D) ^(18.5): 1.5231.

PRODUCTION EXAMPLE 21

[0369] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.126 g of sodium hydride (60% in oil), and 0.47ml of 5-bromo-1-pentene, and according to the process described in theProduction Example 1, there was obtained 0.49 g of2-(4-chlorobenzyl)-2-(4-pentenyl)malononitrile (compound 21).

[0370] Yield: 72%;

[0371] n_(D) ^(22.0): 1.5244.

PRODUCTION EXAMPLE 22

[0372] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.126 g of sodium hydride (60% in oil), and 0.40g of 3-chloro-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.35 g of2-(4-chlorobenzyl)-2-(1-methyl-2-propenyl)malononitrile (compound 22).

[0373] Yield: 55%;

[0374] n_(D) ^(22.5): 1.5284.

PRODUCTION EXAMPLE 23

[0375] Using 2.25 g of (3,4-dichlorobenzyl)malononitrile, 50 ml ofN,N-dimethylformamide, 0.48 g of sodium hydride (60% in oil), and 1.30ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 1.96 g of2-allyl-2-(3,4-dichlorobenzyl)malononitrile (compound 23).

[0376] Yield: 74%;

[0377] m.p.: 71.8° C.

PRODUCTION EXAMPLE 24

[0378] Using 1.13 g of (2,4-dichlorobenzyl)malononitrile, 20 ml ofN,N-dimethylformamide, 0.24 g of sodium hydride (60% in oil), and 0.63ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.78 g of2-allyl-2-(2,4-dichlorobenzyl)malononitrile (compound 24).

[0379] Yield: 59%;

[0380] n_(D) ^(24.5): 1.5447

PRODUCTION EXAMPLE 25

[0381] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.16 g of sodium hydride (60% in oil), and 0.60ml of 1-bromo-3-methyl-2-butene, and according to the process describedin the Production Example 1, there was obtained 0.52 g of2-(4-chlorobenzyl)-2-(3-methyl-2-butenyl)malononitrile (compound 25).

[0382] Yield: 77%;

[0383] n_(D) ^(25.5): 1.5263.

PRODUCTION EXAMPLE 26

[0384] Using 0.80 g of (1-(4-chlorophenyl)-2-methylpropyl)malononitrile,10 ml of N,N-dimethylformamide, 0.21 g of sodium hydride (60% in oil),and 0.70 ml of 4-bromo-1-butene, and according to the process describedin Production Example 1, there was obtained 0.32 g of2-(3-butenyl)-2-(1-(4-chlorophenyl)-2-methylpropyl)malononitrile(compound 26).

[0385] Yield: 32%;

[0386] n_(D) ^(25.5): 1.5217.

PRODUCTION EXAMPLE 27

[0387] Using 0.20 g of (4-(trifluoromethoxy)benzyl)malononitrile, 5 mlof N,N-dimethylformamide, 50 mg of sodium hydride (60% in oil), and 0.19ml of 1-bromo-3-methyl-2-butene, and according to the process describedin Production Example 1, there was obtained 0.19 g of2-(3-methyl-2-butenyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(compound 27).

[0388] Yield: 74%;

[0389] n_(D) ^(24.5): 1.4707.

PRODUCTION EXAMPLE 28

[0390] Using 0.50 g of (3-methoxybenzyl)malononitrile, 10 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 1.1 mlof allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.45 g of2-allyl-2-(3-methoxybenzyl)malononitrile (compound 28).

[0391] Yield: 74%;

[0392] n_(D) ^(22.0): 1.5238.

PRODUCTION EXAMPLE 29

[0393] Using 0.50 g of (4-methoxybenzyl)malononitrile, 10 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 1.1 mlof allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.50 g of2-allyl-2-(4-methoxybenzyl)malononitrile (compound 29).

[0394] Yield: 83%;

[0395] n_(D) ^(22.0): 1.5252.

PRODUCTION EXAMPLE 30

[0396] First, 0.24 g of (4-(trifluoromethoxy)benzylidene)malononitrile,0.66 g of allyltributyltin, and 0.71 g of methyl iodide were dissolvedin 10 ml of benzene, and the solution was heated to the refluxtemperature. Then, 40 mg of azobis(isobutyronitrile) was added, and themixture was stirred for 13 hours, while heating under reflux. Thereaction mixture is poured into a mixture of 40 ml of hexane and 40 mlof acetonitrile, followed by phase separation. The acetonitrile layerwas concentrated, and the resulting residue was subjected to silica gelthin layer chromatography to give 0.19 g of2-allyl-2-(1-(4-(trifluoromethoxy)phenyl)ethyl)malononitrile (compound30).

[0397] Yield: 65%;

[0398]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.68 (3H, d), 2.42-2.61 (2H, m),3.25 (1H, q), 5.23-5.44 (2H, m), 5.83-5.94 (1H, m), 7.25 (2H, d), 7.40(2H, d).

PRODUCTION EXAMPLE 31

[0399] Using 0.24 g of (4-(trifluoromethoxy)benzylidene)malononitrile,10 ml of benzene, 0.66 g of allyltributyltin, 0.89 g ofchloroiodomethane, and 66 mg of azobis(isobutyronitrile), and accordingto the process described in Production Example 30, there was obtained0.20 g of2-allyl-2-(1-(4-(trifluoromethoxy)phenyl)-2-chloroethyl)malononitrile(compound 31).

[0400] Yield: 61%;

[0401]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.43-2.60 (2H, m), 3.43 (1H, dd),4.03 (1H, dd), 4.22 (1H, dd), 5.33-5.53 (2H, m), 5.78-6.01 (1H, m), 7.35(2H, m), 7.41 (2H, m).

PRODUCTION EXAMPLE 32

[0402] Using 0.50 g of(1-(4-(trifluoromethoxy)phenyl)-2-propenyl)malononitrile, 4 ml ofN,N-dimethylformamide, 83 mg of sodium hydride (60% in oil), and 0.51 gof 4-bromo-1-butene, and according to the process described inProduction Example 1, there was obtained 0.56 g of2-(3-butenyl)-2-(1-(4-(trifluoromethoxy)phenyl)-2-propenyl)malononitrile(compound 32).

[0403] Yield: 93%;

[0404]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.77-2.08 (2H, m), 2.41-2.51 (2H,m), 3.67 (1H, d), 5.07-5.18 (2H, m), 5.37-5.51 (2H, m), 5.69-5.82 (1H,m), 5.19-5.33 (1H, m), 7.26 (2H, m), 7.45 (2H, m).

PRODUCTION EXAMPLE 33

[0405] Using 0.25 g of(1-(4-(trifluoromethoxy)phenyl)-2-propenyl)malononitrile, 2 ml ofN,N-dimethylformamide, 42 mg of sodium hydride (60% in oil), and 0.45 gof allyl bromide, and according to the process described in ProductionExample 1, there was obtained 0.25 g of2-allyl-2-(1-(4-(trifluoromethoxy)phenyl)-2-propenyl)malononitrile(compound 33).

[0406] Yield: 87%;

[0407]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.50-2.73 (2H, m), 3.68 (1H, d),5.34-5.52 (4H, m), 5.83-5.97 (1H, m), 6.18-6.33 (1H, m), 7.27 (2H, m),7.46 (2H, m).

PRODUCTION EXAMPLE 34

[0408] Using 0.62 g of(1-(4-(trifluoromethoxy)phenyl)-2-propenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 103 mg of sodium hydride (60% in oil), and 0.56 gof 3-bromo-1-propyne, and according to the process described inProduction Example 1, there was obtained 0.59 g of2-(2-propynyl)-2-(1-(4-(trifluoromethoxy)phenyl)-2-propenyl)malononitrile(compound 34).

[0409] Yield: 83%;

[0410]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.47 (1H, t), 2.74-2.93 (2H, m),3.96 (1H, d), 5.47-5.55 (2H, m), 6.19-6.31 (1H, m), 7.28 (2H, m), 7.49(2H, m).

PRODUCTION EXAMPLE 35

[0411] First, 0.41 g of 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrileand 0.76 g of dibromodifluoromethane was dissolved in 5 ml ofN,N-dimethylformamide, and while stirring under ice-cooling, 80 mg ofsodium hydride (60% in oil) was added, and the mixture was heated to 80°C., followed by stirred for 5 hours. Then, a saturated ammonium chlorideaqueous solution was added to the reaction mixture, which was extracteddiethyl ether. The organic layer was successively washed with water, asaturated sodium chloride aqueous solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 0.16 gof 2-(3-butenyl)-2-(4-(bromodifluoromethoxy)benzyl)malononitrile(compound 35) as a low-polar compound.

[0412] Yield: 25%;

[0413] m.p.: 50.2° C.

[0414] Also given was 58 mg of2-(3-butenyl)-2-(4-(difluoromethoxy)benzyl)malononitrile (compound 36)as a high-polar compound.

[0415] Yield: 12%;

[0416]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.02-2.07(2H, m), 2.44-2.52(2H, m),3.21(2H, s), 5.11-5.20(2H, m), 5.77-5.86(1H, m), 6.54(1H, t), 7.16(2H,d), 7.38(2H, m).

PRODUCTION EXAMPLE 36

[0417] Using 0.43 g of (3,4-(methylenedioxy)benzyl)malononitrile, 5 mlof N,N-dimethylformamide, 100 mg of sodium hydride (60% in oil), and0.36 g of 4-bromo-1-butene, and according to the process described inProduction Example 1, there was obtained 0.42 g of2-(3-butenyl)-2-(3,4-(methylenedioxy)benzyl)malononitrile (compound 37).

[0418] Yield: 76%;

[0419]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.99-2.05 (2H, m), 2.45-2.48 (2H,m), 3.14 (2H, s), 5.09-5.20 (2H, m), 5.72-5.90 (1H, m), 6.00 (2H, s),6.82-6.85 (3H, m).

PRODUCTION EXAMPLE 37

[0420] First, 0.30 g of 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrileand 0.19 g of allyl bromide was dissolved in 5 ml ofN,N-dimethylformamide, and 0.22 g of potassium carbonate was added,followed by stirred overnight at room temperature. Then, water was addedto the reaction mixture, which was extracted diethyl ether. The organiclayer was successively washed with water, a saturated sodium chlorideaqueous solution, dried over anhydrous magnesium sulfate, and thenconcentrated under reduced pressure. The residue was subjected to silicagel column chromatography to give 0.34 g of2-(3-butenyl)-2-(4-(2-propenyloxy)benzyl)malononitrile (compound 38).

[0421] Yield: 96%;

[0422] m.p.: 77.7° C.

PRODUCTION EXAMPLE 38

[0423] First, 0.48 g of 4-(trifluoromethoxy)benzylidenemalononitrile,0.10 g of tetrakis(triphenylphosphine)palladium, and 0.26 g ofallylmethyl carbonate were dissolved in 20 ml of tetrahydrofuran, andthe solution was stirred at room temperature for 10 hours. Then, theresidue obtained by concentration under reduced pressure was subjectedto silica gel chromatography to give 0.56 g of2-allyl-2-(4-(trifluoromethoxy)-α-methoxybenzyl)malononitrile (compound39).

[0424] Yield: 89%;

[0425]₁H-NMR (CDCl₃, TMS, δ (ppm)): 2.66-2.79 (2H, m), 3.36 (3H, s),4.43 (1H, s), 5.38-5.46 (2H, m), 5.85-5.99 (1H, m), 7.32 (2H, d), 7.53(2H, d).

PRODUCTION EXAMPLE 39

[0426] Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 6ml of N,N-dimethylformamide, 90 mg of sodium hydride (60% in oil), and0.29 g of allyl bromide, and according to the process described inProduction Example 1, there was obtained 0.49 g of2-allyl-2-(4-(trifluoromethylthio)benzyl)malononitrile (compound 41).

[0427] Yield: 84%;

[0428]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.69-2.75 (2H, m), 3.21 (2H, s),5.39-5.51 (2H, m), 5.88-6.02 (1H, m), 7.45 (2H, d), 7.70 (2H, d).

PRODUCTION EXAMPLE 40

[0429] Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 6ml of N,N-dimethylformamide, 90 mg of sodium hydride (60% in oil), and0.32 g of 4-bromo-1-butene, and according to the process described inProduction Example 1, there was obtained 0.26 g of2-(3-butenyl)-2-(4-(trifluoromethylthio)benzyl)malononitrile (compound42).

[0430] Yield: 44%;

[0431]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.04-2.10 (2H, m), 2.45-2.54 (2H,m), 3.25 (2H, s), 5.10-5.22 (2H, m), 5.74-5.87 (1H, m), 7.45 (2H, d),7.71 (2H, m).

PRODUCTION EXAMPLE 41

[0432] Using 0.51 g of 4-(trifluoromethylthio)benzylidenemalononitrile,0.10 g of tetrakis(triphenylphosphine)palladium, 0.26 g of allylmethylcarbonate, and 20 ml of tetrahydrofuran, and according to the processdescribed in Production Example 38, there was obtained 0.49 g of2-allyl-2-(4-(trifluoromethylthio)-α-methoxybenzyl)malononitrile(compound 43).

[0433] Yield: 75%;

[0434]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.72-2.76 (2H, m), 3.38 (3H, s),4.46 (1H, s), 5.38-5.48 (2H, m), 5.79-5.94 (1H, m), 7.56 (2H, m), 7.76(2H, m).

PRODUCTION EXAMPLE 42

[0435] Using 1.76 g of (4-ethoxybenzyl)malononitrile, 30 ml ofN,N-dimethylformamide, 0.40 g of sodium hydride (60% in oil), and 4.2 mlof allyl bromide, and according to the process described in theProduction Example 1, there was obtained 1.30 g of2-allyl-2-(4-ethoxybenzyl)malononitrile (compound 44).

[0436] Yield: 54%;

[0437] m.p.: 84.3° C.

PRODUCTION EXAMPLE 43

[0438] Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 6 mlof N,N-dimethylformamide, 95 mg of sodium hydride (60% in oil), and 0.47g of isopentyl bromide, and according to the process described inProduction Example 1, there was obtained 0.42 g of2-(3-methylbutyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile (compound45).

[0439] Yield: 65%;

[0440]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.96 (3H, d), 1.59-1.65 (3H, m),1.94-2.01 (2H, m), 3.20 (2H, s), 7.26 (2H, d), 7.43 (2H, d).

PRODUCTION EXAMPLE 44

[0441] Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 6ml of N,N-dimethylformamide, 90 mg of sodium hydride (60% in oil), and0.21 g of 1-chloro-2-butene, and according to the process described inProduction Example 1, there was obtained 0.40 g of2-(2-butenyl)-2-(4-(trifluoromethylthio)benzyl)malononitrile (compound46).

[0442] Yield: 66%;

[0443]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.72 (3H, dd, Z), 1.80 (3H, dd, E),2.68 (2H, d, E), 2.73 (2H, d, Z), 3.18 (2H, s, Z), 3.19 (2H, s, E),5.49-5.68 (1H, m, E, Z), 5.78-6.00 (1H, m, E, Z), 7.45 (2H, d, E, Z),7.70 (2H, d, E, Z).

PRODUCTION EXAMPLE 45

[0444] Using 0.50 g of (4-(trifluoromethylthio)benzyl)malononitrile, 6ml of N,N-dimethylformamide, 90 mg of sodium hydride (60% in oil), and0.21 g of 3-chloro-1-butene, and according to the process described inProduction Example 1, there was obtained 0.14 g of2-(1-methyl-2-propenyl)-2-(4-(trifluoromethylthio)benzyl)malononitrile(compound 47).

[0445] Yield: 24%;

[0446]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.47 (3H, d), 2.62-2.74 (1H, m),3.19 (2H, dd), 5.35-5.46 (2H, m), 5.80-5.95 (2H, m), 7.45 (2H, d), 7.69(2H, d).

PRODUCTION EXAMPLE 46

[0447] Using 1.93 g of (1-(3-chlorophenyl)-1-methylethyl)malononitrile,30 ml of N,N-dimethylformamide, 0.39 g of sodium hydride (60% in oil),and 3.70 ml of allyl bromide, and according to the process described inthe Production Example 1, there was obtained 1.14 g of2-allyl-2-(1-(3-chlorophenyl)-1-methylethyl)malononitrile (compound 48).

[0448] Yield: 50%;

[0449] m.p.: 84.3° C.

PRODUCTION EXAMPLE 47

[0450] Using 0.60 g of (1-(2-chlorophenyl)-1-methylethyl)malononitrile,10 ml of N,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil),and 1.2 ml of allyl bromide, and according to the process described inthe Production Example 1, there was obtained 0.60 g of2-allyl-2-(1-(2-chlorophenyl)-1-methylethyl)malononitrile (compound 49).

[0451] Yield: 71%;

[0452] n_(D) ^(23.5): 1.5398.

PRODUCTION EXAMPLE 48

[0453] Using 2.01 g of (4-nitrobenzyl)malononitrile, 50 ml ofN,N-dimethylformamide, 0.44 g of sodium hydride (60% in oil), and 4.23ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 1.13 g of2-allyl-2-(4-nitrobenzyl)malononitrile (compound 50).

[0454] Yield: 47%;

[0455] m.p.: 94.2° C.

PRODUCTION EXAMPLE 49

[0456] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.12 g of sodium hydride (60% in oil), and 0.27ml of isopropyl iodide, and according to the process described in theProduction Example 1, there was obtained 0.19 g of2-(4-chlorobenzyl)-2-isopropylmalononitrile (compound 51).

[0457] Yield: 31%;

[0458] n_(D) ^(22.5): 1.5229.

PRODUCTION EXAMPLE 50

[0459] Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 21 mlof N,N-dimethylformamide, 100 mg of sodium hydride (60% in oil), and0.45 g of 4-bromo-1-butene, and according to the process described inProduction Example 1, there was obtained 0.25 g of2-(3-butenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 52).

[0460] Yield: 20%;

[0461]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.05-2.10 (2H, m), 2.46-2.52 (2H,m), 3.28 (2H, s), 5.12-5.22 (2H, m), 5.77-5.86 (1H, m), 7.52 (2H, d),7.69 (2H, d).

PRODUCTION EXAMPLE 51

[0462] Using 2.25 g of (2,3-dichlorobenzyl)malononitrile, 20 ml ofN,N-dimethylformamide, 0.48 g of sodium hydride (60% in oil), and 1.30ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 1.72 g of2-allyl-2-(2,3-dichlorobenzyl)malononitrile (compound 53).

[0463] Yield: 65%;

[0464] n_(D) ^(23.5): 1.5448.

PRODUCTION EXAMPLE 52

[0465] Using 2.25 g of (2,6-dichlorobenzyl)malononitrile, 20 ml ofN,N-dimethylformamide, 0.48 g of sodium hydride (60% in oil), and 1.30ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 2.00 g of2-allyl-2-(2,6-dichlorobenzyl)malononitrile (compound 54).

[0466] Yield: 75%;

[0467] n_(D) ^(23.5): 1.5483.

PRODUCTION EXAMPLE 53

[0468] First, 0.50 g of 4-(trifluoromethylthio)benzylidenemalononitrile,60 mg of tris(dibenzylideneacetone)dipalladium-chloroform complex, and0.11 g of 1,1′-bis(diphenylphosphino)ferrocene were added to 10 ml oftetrahydrofuran, and 0.30 g of allyl chloride and 0.39 g oftrimethylsilyl cyanide were further added under an atmosphere ofnitrogen, followed by stirring at 75° C. for a day. The reaction mixturewas then filtered through silica gel and the filtrate was concentrated.The residue was subjected to silica gel chromatography to give 0.42 g of2-allyl-2-(4-(trifluoromethylthio)-α-cyanobenzyl)malononitrile (compound56).

[0469] Yield: 67%;

[0470]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.92-3.12 (2H, m), 4.29 (1H, s),5.59-5.65 (2H, m), 5.81-5.98 (1H, m), 7.63 (2H, d), 7.82 (2H, d).

PRODUCTION EXAMPLE 54

[0471] Using 0.47 g of 4-(trifluoromethoxy)benzylidenemalononitrile, 60mg of tris(dibenzylideneacetone)dipalladium-chloroform complex, 0.11 gof 1,1′-bis(diphenylphosphino)ferrocene, 10 ml of tetrahydrofuran, 0.30g of allyl chloride, and 0.39 g of trimethylsilyl cyanide, and accordingto the process described in Production Example 53, there was obtained0.42 g of 2-allyl-2-(4-(trifluoromethoxy)-α-cyanobenzyl)malononitrile(compound 55).

[0472] Yield: 70%;

[0473]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.92-3.10 (2H, m), 4.27 (1H, s),5.58-5.63 (2H, m), 5.91-5.97 (1H, m), 7.37 (2H, d), 7.62 (2H, d).

PRODUCTION EXAMPLE 55

[0474] Using 0.30 g of allylmalononitrile, 4 ml ofN,N-dimethylformamide, 130 mg of sodium hydride (60% in oil), and 0.99 gof 2,4-bis(trifluoromethyl)benzyl bromide, and according to the processdescribed in Production Example 1, there was obtained 0.70 g of2-allyl-2-(2,4-bis(trifluoromethyl)benzyl)malononitrile (compound 57).

[0475] Yield: 72%;

[0476]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.82 (2H, d), 3.47 (2H, s),5.45-5.58 (2H, m), 5.89-6.05 (1H, m), 7.92 (1H, d), 7.98 (1H, d), 8.02(1H, s).

PRODUCTION EXAMPLE 56

[0477] Using 0.30 g of allylmalononitrile, 4 ml ofN,N-dimethylformamide, 125 mg of sodium hydride (60% in oil), and 0.85g. of 2-chloro-4-(trifluoromethyl)benzyl bromide, and according to theprocess described in Production Example 1, there was obtained 0.40 g of2-allyl-2-(2-chloro-4-(trifluoromethyl)benzyl)malononitrile (compound58).

[0478] Yield: 47%;

[0479]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.84 (2H, d), 3.51 (2H, s),5.41-5.56 (2H, m), 5.88-6.07 (1H, m), 7.62 (1H, d), 7.71 (1H, d), 7.83(1H, s).

PRODUCTION EXAMPLE 57

[0480] Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 3 mlof N,N-dimethylformamide, 93 mg of sodium hydride (60% in oil), and 0.42g of 1-bromo-2-butyne, and according to the process described inProduction Example 1, there was obtained 0.47 g of2-(2-butynyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile (compound 59).

[0481] Yield: 70%;

[0482]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.93 (3H, t), 2.85 (2H, q), 3.33(2H, s), 7.25 (2H, d), 7.45 (2H, d).

PRODUCTION EXAMPLE 58

[0483] Using 0.30 g of (3-butenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 110 mg of sodium hydride (60% in oil), and 0.75 gof 2-chloro-4-(trifluoromethyl)benzyl bromide, and according to theprocess described in Production Example 1, there was obtained 0.30 g of2-(3-butenyl)-2-(2-chloro-4-(trifluoromethyl)benzyl)malononitrile(compound 60).

[0484] Yield: 39%;

[0485]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.10-2.17 (2H, m), 2.49-2.52 (2H,m), 3.53 (2H, s), 5.11-5.22 (2H, m), 5.72-5.88 (1H, m), 7.62 (1H, d),7.70 (1H, d), 7.75 (1H, s).

PRODUCTION EXAMPLE 59

[0486] Using 0.60 g of allylmalononitrile, 8 ml ofN,N-dimethylformamide, 255 mg of sodium hydride (60% in oil), and 1.55 gof 4-(methylsulfonyl)benzyl bromide, and according to the processdescribed in Production Example 1, there was obtained 0.64 g of2-allyl-2-(4-(methylsulfonyl)benzyl)malononitrile (compound 61).

[0487] Yield: 41%;

[0488]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.78 (2H, d), 3.10 (3H, s), 3.29(2H, s), 5.45-5.53 (2H, m), 5.88-6.07 (1H, m), 7.61 (2H, d), 8.01 (2H,d).

PRODUCTION EXAMPLE 60

[0489] Using 1.23 g of (2,3,4,5,6-pentafluorobenzyl)malononitrile, 20 mlof N,N-dimethylformamide, 0.24 g of sodium hydride (60% in oil), and0.63 ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.98 g of2-allyl-2-(2,3,4,5,6-pentafluorobenzyl)malononitrile (compound 62).

[0490] Yield: 68%;

[0491] m.p.: 78.2° C.

PRODUCTION EXAMPLE 61

[0492] Using 0.15 g of allylmalononitrile, 5 ml ofN,N-dimethylformamide, 62 mg of sodium hydride (60% in oil), and 0.43 gof 2-nitro-4-(trifluoromethyl)benzyl bromide, and according to theprocess described in Production Example 1, there was obtained 0.32 g of2-allyl-2-(2-nitro-4-(trifluoromethyl)benzyl)malononitrile (compound63).

[0493] Yield: 70%;

[0494]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.88 (2H, d), 3.80 (2H, s),5.46-5.57 (2H, m), 5.88-6.05 (1H, m), 7.82 (1H, d), 7.94 (1H, d), 8.46(1H, s).

PRODUCTION EXAMPLE 62

[0495] Using 0.15 g of allylmalononitrile, 5 ml ofN,N-dimethylformamide, 62 mg of sodium hydride (60% in oil), and 0.44 gof 2,6-dichloro-4-(trifluoromethyl)benzyl bromide, and according to theprocess described in Production Example 1, there was obtained 0.20 g of2-allyl-2-(2,6-dichloro-4-(trifluoromethyl)benzyl)malononitrile(compound 64).

[0496] Yield: 43%;

[0497]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.94 (2H, d), 3.75 (1H, s),5.50-5.58 (2H, m), 5.95-6.10 (1H, s), 7.71 (2H, s).

PRODUCTION EXAMPLE 63

[0498] Using 0.15 g of (3-butenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 55 mg of sodium hydride (60% in oil), and 0.39 gof 2,6-dichloro-4-(trifluoromethyl)benzyl bromide, and according to theprocess described in Production Example 1, there was obtained 95 mg of2-(3-butenyl)-2-(2,6-dichloro-4-(trifluoromethyl)benzyl)malononitrile(compound 65).

[0499] Yield: 22%;

[0500]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.22-2.28 (2H, m), 2.49-2.57 (2H,m), 3.77 (2H, s), 5.13-5.23 (2H, m), 5.78-5.90 (1H, m), 7.69 (2H, s).

PRODUCTION EXAMPLE 64

[0501] Using 0.41 g of (1-(3-chlorophenyl)-2-methylpropyl)malononitrile,5 ml of N,N-dimethylformamide, 85 mg of sodium hydride (60% in oil), and0.22 ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.35 g of2-allyl-2-(1-(3-chlorophenyl)-2-methylpropyl)malononitrile (compound66).

[0502] Yield: 73%;

[0503] n_(D) ^(23.0): 1.5267.

PRODUCTION EXAMPLE 65

[0504] Using 97 mg of (3-butenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 37 mg of sodium hydride (60% in oil), and 0.25 gof 2-nitro-4-(trifluoromethyl)benzyl bromide, and according to theprocess described in Production Example 1, there was obtained 0.12 g of2-(3-butenyl)-2-(2-nitro-4-(trifluoromethyl)benzyl)malononitrile(compound 67).

[0505] Yield: 43%;

[0506]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.21-2.29 (2H, m), 2.54-2.65 (2H,m), 5.64-5.76 (2H, m), 5.82-5.98 (1H, m), 7.33 (1H, d), 8.03 (1H, m),8.45 (1H, s).

PRODUCTION EXAMPLE 66

[0507] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.16 g of sodium hydride (60% in oil), and 0.33ml of methyl iodide, and according to the process described in theProduction Example 1, there was obtained 0.23 g of2-(4-chlorobenzyl)-2-methylmalononitrile (compound 68).

[0508] Yield: 43%;

[0509] m.p.: 91.1° C.

PRODUCTION EXAMPLE 67

[0510] Using 0.30 g of allylmalononitrile, 4 ml ofN,N-dimethylformamide, 124 mg of sodium hydride (60% in oil), and 0.80 gof 3-fluoro-4-(trifluoromethyl)benzyl bromide, and according to theprocess described in Production Example 1, there was obtained 0.37 g of2-allyl-2-(3-fluoro-4-(trifluoromethyl)benzyl)malononitrile (compound69).

[0511] Yield: 46%;

[0512]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.77 (2H, d), 3.23 (2H, s),5.43-5.54 (2H, m), 5.86-5.98 (1H, m), 7.25 (1H, m), 7.29 (1H, d),7.65-7.72 (1H, m).

PRODUCTION EXAMPLE 68

[0513] Using 0.30 g of allylmalononitrile, 6 ml ofN,N-dimethylformamide, 124 mg of sodium hydride (60% in oil), and 0.68 gof 4-(methylthio)benzyl bromide, and according to the process describedin Production Example 1, there was obtained 0.42 g of2-allyl-2-(4-(methylthio)benzyl)malononitrile (compound 70).

[0514] Yield: 62%;

[0515]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.49 (3H, s), 2.70 (2H, s), 3.16(2H, s), 5.38-5.47 (2H, m), 5.80-5.99 (1H, m), 7.27 (2H, d), 7.28 (2H,d).

PRODUCTION EXAMPLE 69

[0516] Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 6 ml ofN,N-dimethylformamide, 98 mg of sodium hydride (60% in oil), and 0.41 gof 1-iodopropane, and according to the process described in ProductionExample 1, there was obtained 0.21 g of2-propyl-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 71).

[0517] Yield: 41%;

[0518]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.06 (3H, t), 1.68-1.77 (2H, m),1.88-1.96 (2H, m), 7.48 (2H, d), 7.63 (2H, m).

PRODUCTION EXAMPLE 70

[0519] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.16 g of sodium hydride (60% in oil), and 0.39ml of ethyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.20 g of2-(4-chlorobenzyl)-2-ethylmalononitrile (compound 72).

[0520] Yield: 35%;

[0521] m.p.: 70.9° C.

PRODUCTION EXAMPLE 71

[0522] Using 0.50 g of (4-chlorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.16 g of sodium hydride (60% in oil), and 0.85 gof (Z)-1-bromo-3-hexene, and according to the process described in theProduction Example 1, there was obtained 0.22 g of2-(4-chlorobenzyl)-2-((Z)-3-hexenyl)malononitrile (compound 73).

[0523] Yield: 31%;

[0524] m.p.: 44.8° C.

PRODUCTION EXAMPLE 72

[0525] Using 0.56 g of (1-(4-chlorophenyl)ethyl)malononitrile, 5 ml ofN,N-dimethylformamide, 160 mg of sodium hydride (60% in oil), and 0.46ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.29 g of2-allyl-2-(1-(4-chlorophenyl)ethyl)malononitrile (compound 74).

[0526] Yield: 43%;

[0527] n_(D) ^(25.5): 1.5294.

PRODUCTION EXAMPLE 73

[0528] Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 6 ml ofN,N-dimethylformamide, 98 mg of sodium hydride (60% in oil), and 0.27 gof bromoethane, and according to the process described in ProductionExample 1, there was obtained 0.33 g of2-ethyl-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 75).

[0529] Yield: 58%;

[0530]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.35 (2H, t), 2.06 (2H, q), 3.26(2H, s), 7.52 (2H, d), 7.68 (2H, d).

PRODUCTION EXAMPLE 74

[0531] Using 0.56 g of (1-(4-chlorophenyl)ethyl)malononitrile, 5 ml ofN,N-dimethylformamide, 160 mg of sodium hydride (60% in oil), and 0.65ml of 1-bromo-4-pentene, and according to the process described in theProduction Example 1, there was obtained 0.25 g of2-(1-(4-chlorophenyl)ethyl)-2-(4-pentenyl)malononitrile (compound 76).

[0532] Yield: 33%;

[0533] n_(D) ^(25.5): 1.5204.

PRODUCTION EXAMPLE 75

[0534] Using 0.50 g of (4-methylbenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.18 g of sodium hydride (60% in oil), and 0.50ml of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.37 g of2-allyl-2-(4-methylbenzyl)malononitrile (compound 77).

[0535] Yield: 60%;

[0536] m.p.: 74.5° C.

PRODUCTION EXAMPLE 76

[0537] First, 0.40 g of 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrileand 0.22 g of acetic anhydride was dissolved in 5 ml of toluene, towhich 0.23 g of triethylamine was added, followed by stirring overnightat room temperature. Then, water was added to the reaction mixture,which was extracted with diethyl ether. The organic layer wassuccessively washed with a saturated ammonium chloride aqueous solution,a saturated sodium bicarbonate aqueous solution, a saturated sodiumchloride aqueous solution, dried over anhydrous magnesium sulfate, andthen concentrated under reduced pressure. The residue was subjected tosilica gel column chromatography to give 0.45 g of2-(3-butenyl)-2-(4-(acetyloxy)benzyl)malononitrile (compound 78).

[0538] Yield: 95%;

[0539] m.p.: 80.2° C.

PRODUCTION EXAMPLE 77

[0540] Using 0.50 g of (4-(trifluoromethyl)benzyl)malononitrile, 10 mlof N,N-dimethylformamide, 89 mg of sodium hydride (60% in oil), and 0.33g of 5-bromo-1-pentene, and according to the process described inProduction Example 1, there was obtained 0.16 g of2-(4-pentenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 79).

[0541] Yield: 25%;

[0542]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.84-1.87 (2H, m), 1.96-2.02 (2H,m), 2.18 (2H, t), 3.25 (2H, s), 5.05-5.11 (2H, m), 5.76-5.86 (1H, m),7.51 (2H, d), 7.58 (2H, d).

PRODUCTION EXAMPLE 78

[0543] First, 0.40 g of 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrilewas dissolved in 5 ml of N,N-dimethylformamide, to which 75 mg of sodiumhydride (60% in oil) was added, while stirring under ice cooling. Afterthe evolution of hydrogen gas ceased, while stirring under ice cooling,0.49 g of 1,1,2,2-tetrafluoro-1-iodoethane was added dropwise, followedby further stirring at room temperature overnight. Then, a saturatedammonium chloride aqueous solution was added to the reaction mixture,which was extracted with diethyl ether. The organic layer wassuccessively washed with water, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 82 mg of2-(3-butenyl)-2-(4-(1,1,2,2-tetrafluoroethoxy)benzyl)malononitrile(compound 80).

[0544] Yield: 14%;

[0545] m.p.: 60.5° C.

PRODUCTION EXAMPLE 79

[0546] Using 0.40 g of 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrile, 5ml of N,N-dimethylformamide, 75 mg of sodium hydride (60% in oil), and0.45 g of 2,2,2-trifluoro-1-iodoethane, and according to the processdescribed in the Production Example 78, there was obtained 70 mg of2-(3-butenyl)-2-(4-(2,2,2-trifluoroethoxy)benzyl)malononitrile (compound81).

[0547] Yield: 13%;

[0548] m.p.: 58.0° C.

PRODUCTION EXAMPLE 80

[0549] First, 0.48 g of (4-(trifluoromethoxy)benzyliden)malononitrileand 1.0 g of ethanol was dissolved in 20 ml of tetrahydrofuran, to which0.10 g of tetrakis(triphenylphosphine)palladium and 0.26 g of allylmethyl carbonate was added, followed by further stirring for 10 hours atroom temperature. Then, the reaction mixture was concentrated underreduced pressure. The residue was subjected to silica gel columnchromatography to give 0.65 g of2-allyl-2-(4-(trifluoromethoxy)-α-ethoxybenzyl)malononitrile (compound82).

[0550] Yield: 99%;

[0551]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.26(3H, t), 2.66-2.79(2H, m),3.36-3.57(2H, m), 4.54(1H, s), 5.38-5.46(2H, m), 5.87-5.99(1H, m),7.30(2H, d), 7.55(2H, d).

PRODUCTION EXAMPLE 81

[0552] Using 0.36 g of (4-cyanobenzyliden)malononitrile, 0.10 g oftetrakis(triphenylphosphine)palladium, and 0.26 g of allyl methylcarbonate, and 20 ml of tetrahydrofuran, and according to the processdescribed in the Production Example 38, there was obtained 0.11 g of2-allyl-2-(4-cyano-α-methoxybenzyl)malononitrile (compound 83).

[0553] Yield: 22%;

[0554]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.72-2.81(2H, m), 3.38(3H, s),4.47(1H, s), 5.39-5.49(2H, m), 5.80-5.98(1H, m), 7.64(2H, d), 7.79(2H,d).

PRODUCTION EXAMPLE 82

[0555] Using 0.38 g of (4-chlorobenzyliden)malononitrile, 0.10 g oftetrakis(triphenylphosphine)palladium, and 0.26 g of allyl methylcarbonate, and 20 ml of tetrahydrofuran, and according to the processdescribed in the Production Example 38, there was obtained 0.44 g of2-allyl-2-(4-chloro-α-methoxybenzyl)malononitrile (compound 84).

[0556] Yield: 84%;

[0557]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.65-2.76(2H, m), 3.35(3H, s),4.41(1H, s), 5.37-5.47(2H, m), 5.85-6.00(1H, m), 7.45(4H, bs).

PRODUCTION EXAMPLE 83

[0558] Using 0.41 g of (2,2-dimethylpropyl)malononitrile, 7 ml ofN,N-dimethylformamide, 0.13 g of sodium hydride (60% in oil), and 0.92 gof 4-(trifluoromethyl)benzyl bromide, and according to the processdescribed in the Production Example 1, there was obtained 0.59 g of2-(2,2-dimethylpropyl)-2-(4-(trifluoromethoxy)benzyl)malononitrile(compound 85).

[0559] Yield: 63%;

[0560]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.20(9H, s), 1.94(2H, s), 3.21(2H,s), 7.26(2H, d), 7.44(2H, d).

PRODUCTION EXAMPLE 84

[0561] Using 1.36 g of (2,2-dimethylpropyl)malononitrile, 20 ml ofN,N-dimethylformamide, 0.43 g of sodium hydride (60% in oil), and 3.00 gof 4-bromobenzyl bromide, and according to the process described in theProduction Example 1, there was obtained 2.74 g of2-(4-bromobenzyl)-2-(2,2-dimethylpropyl)malononitrile (compound 86).

[0562] Yield: 90%;

[0563]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.19(9H, s), 1.91(2H, s), 3.16(2H,s), 7.28(2H, d), 7.54(2H, d).

PRODUCTION EXAMPLE 85

[0564] Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 8 mlof N,N-dimethylformamide, 96 mg of sodium hydride (60% in oil), and 0.57g of isobytyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.31 g of2-isobutyl-2-(4-(trifluoromethoxy)benzyl)malononitrile (compound 87).

[0565] Yield: 51%;

[0566]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.13(6H, d), 1.88(2H, d), 2.13(1H,hept), 3.20(2H, s), 7.26(2H, d), 7.43(2H, d).

PRODUCTION EXAMPLE 86

[0567] Using 0.50 g of (4-(trifluoromethoxy)benzyl)malononitrile, 8 mlof N,N-dimethylformamide, 96 mg of sodium hydride (60% in oil), and 0.63g of pentyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.45 g of2-pentyl-2-(4-(trifluoromethoxy)benzyl)malononitrile (compound 88).

[0568] Yield: 70%;

[0569]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.93(3H, t), 1.29-1.49(4H, m),1.62-1.80(2H, m), 1.92-1.99(2H, m), 3.20(2H, s), 7.26(2H, d), 7.41(2H,d).

PRODUCTION EXAMPLE 87

[0570] Using 0.50 g of (3-(trifluoromethoxy)benzyl)malononitrile, 20 mlof N,N-dimethylformamide, 92 mg of sodium hydride (60% in oil), and 0.38g of allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.54 g of2-allyl-2-(3-(trifluoromethoxy)benzyl)malononitrile (compound 89).

[0571] Yield: 93%;

[0572]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.70-2.75(2H, m), 3.21(2H, s),5.30-5.51(2H, m), 5.86-6.02(1H, m), 7.25-7.50(4H, m).

PRODUCTION EXAMPLE 88

[0573] Using 0.50 g of (3-(trifluoromethoxy)benzyl)malononitrile, 20 mlof N,N-dimethylformamide, 92 mg of sodium hydride (60% in oil), and 420mg of 4-bromo-1-butene, and according to the process described in theProduction Example 1, there was obtained 0.28 g of2-(3-butenyl)-2-(3-(trifluoromethoxy)benzyl)malononitrile (compound 90).

[0574] Yield: 46%;

[0575]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.00-2.09(2H, m), 2.41-2.53(2H, m),3.24(2H, s), 5.07-5.21(2H, m), 5.73-5.89(1H, m), 7.25-7.50(4H, m).

PRODUCTION EXAMPLE 89

[0576] First, 1.0 g of (4-methoxybenzylidene)malononitrile was dissolvedin 30 ml of tetrahydrofuran, to which 0.57 g of trimethylsilyl cyanidewas added at room temperature under a atmosphere of nitrogen, followedby stirred for 30 minutes. Then, 5.5 ml of tetrabutylammonium fluoride(1.0 M solution of tetrahydrofuran) was added dropwise to the mixtureunder ice-cooling, followed by stirred for 4 hours keeping ice-cooling.Then, 0.98 g of allyl bromide was added dropwise followed by stirringovernight at room temperature. Then, a saturated ammonium chlorideaqueous solution was added to the reaction mixture, which was extracteddiethyl ether. The organic layer was successively washed with water, asaturated sodium chloride aqueous solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 1.0 gof 2-allyl-2-(4-methoxy-α-cyanobenzyl)malononitrile (compound 91).

[0577] Yield: 76%;

[0578]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.98(2H, ddd), 3.85(3H, s), 4.26(1H,s), 5.54-5.62(2H, m), 5.87-6.07(1H, m), 7.04(2H, d), 7.47(2H, d).

PRODUCTION EXAMPLE 90

[0579] Using 1.0 g of (4-methylbenzyliden)malononitrile, 30 ml oftetrahydrofuran, 0.62 g of trimethylsilyl cyanide, 6.0 ml oftetrabutylammonium fluoride (1.0 M solution of tetrahydrofuran), and1.08 g of allyl bromide, and according to the process described in theProduction Example 89, there was obtained 1.0 g of2-allyl-2-(4-methyl-α-cyanobenzyl)malononitrile (compound 92).

[0580] Yield: 76%;

[0581]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.41(3H, s), 2.96(2H, ddd), 4.23(1H,s), 5.54-5.60(2H, m), 5.87-6.01(1H, m), 7.31(2H, d), 7.43(2H, d).

PRODUCTION EXAMPLE 91

[0582] Using 0.50 g of (4-(methoxycarbonyl)benzylidene)malononitrile, 70mg of tris(dibenzylideneacetone)dipalladium-chloroform complex, 0.14 gof 1,1′-bis(diphenylphosphino)ferrocene, 12 ml of tetrahydrofuran, and0.37 g of allyl chloride, and according to the process described in theProduction Example 53, there was obtained 0.31 g of2-allyl-2-(4-(methoxycarbonyl)-α-cyanobenzyl)malononitrile (compound93).

[0583] Yield: 48%;

[0584]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.92-3.13(2H, m), 3.96(3H, s),4.32(1H, s), 5.57-5.65(2H, m), 5.89-6.03(1H, m), 7.65(2H, d), 8.19(2H,d).

PRODUCTION EXAMPLE 92

[0585] Using 0.3 g of (3-butenyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.72 gof 3,5-bis(trifluoromethyl)benzyl bromide, and according to the processdescribed in the Production Example 1, there was obtained 0.12 g of2-(3,5-bis(trifluoromethyl)benzyl)-2-(3-butenyl)malononitrile (compound94).

[0586] Yield: 14%;

[0587]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.08-2.13(2H, m), 2.48-2.56(2H, m),3.34(2H, s), 5.14-5.23(2H, m), 5.78-5.87(1H, m), 7.86(2H, s), 7.95(1H,s).

PRODUCTION EXAMPLE 93

[0588] First, 0.72 g of 2,3-dimethoxybenzyl bromide was dissolved in 3ml of N,N-dimethylformamide, to which a suspension 0.05 g of sodiumhydride (60% in oil) and 0.3 g of allylmalononitrile in 2 ml ofN,N-dimethylformamide was added dropwise, while stirring under icecooling, followed by further stirring at 0° C. for 4 hours. Then, 10%hydrochloric acid was added to the reaction mixture, which was extractedwith ethyl acetate. The organic layer was successively washed withwater, a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was subjected to silica gel column chromatographyto give 0.34 g of 2-allyl-2-(2,3-dimethoxybenzyl)malononitrile (compound95).

[0589] Yield: 46%;

[0590]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.67(2H, d), 3.31(2H, s), 3.88(3H,s), 3.90(3H, s), 5.37-5.94(2H, m), 5.84-6.01(1H, s), 6.90-7.06(3H, m).

PRODUCTION EXAMPLE 94

[0591] Using 0.47 g of 4-vinylbenzyl chloride, 5 ml ofN,N-dimethylformamide, 0.13 g of sodium hydride (60% in oil), and 0.3 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.22 g of2-allyl-2-(4-vinylbenzyl)malononitrile (compound 96).

[0592] Yield: 35%;

[0593]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.69(2H, d), 3.19(2H, s), 5.29(1H,dd), 5.44(2H, dd), 5.77(1H, dd), 5.89-6.04(1H, m), 6.72(1H, dd),7.33(2H, d), 7.44(2H, d).

PRODUCTION EXAMPLE 95

[0594] Using 0.40 g of 4-acetylbenzyl chloride, 5 ml ofN,N-dimethylformamide, 0.08 g of sodium hydride (60% in oil), and 0.2 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.25 g of2-(4-acetylbenzyl)-2-allylmalononitrile (compound 97).

[0595] Yield: 56%;

[0596]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.63(3H, s), 2.73(2H, d), 3.22(2H,s), 4.89-5.02(2H, m), 5.87-6.05(1H, m), 7.49(2H, d), 7.97(2H, d).

PRODUCTION EXAMPLE 96

[0597] Using 0.3.0 g of 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrile,5 ml of N,N-dimethylformamide, 60 mg of sodium hydride (60% in oil), and0.18 g of ethyl bromide, and according to the process described in theProduction Example 78, there was obtained 255 mg of2-(3-butenyl)-2-(4-ethoxybenzyl)malononitrile (compound 98).

[0598] Yield: 75%;

[0599]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.42(3H, t), 1.96-2.04(2H, m),2.39-2.55(2H, m), 3.17(2H, s), 4.04(2H, q), 5.08-5.19(2H, m),5.71-5.92(1H, m), 6.90(2H, bd), 7.27(2H, bd).

PRODUCTION EXAMPLE 97

[0600] Using 0.30 g of 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrile, 5ml of N,N-dimethylformamide, 60 mg of sodium hydride (60% in oil), and0.28 g of propyl iodide, and according to the process described in theProduction Example 78, there was obtained 215 mg of2-(3-butenyl)-2-(4-propoxybenzyl)malononitrile (compound 99).

[0601] Yield: 60%;

[0602]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.04(3H, t), 1.72-1.87(2H, m),1.97-2.04(2H, m), 2.41-2.50(2H, m), 3.17(2H, s), 3.92(2H, t),5.08-5.20(2H, m), 5.70-5.90(1H, m), 6.90(2H, bd), 7.27(2H, bd).

PRODUCTION EXAMPLE 98

[0603] Using 0.30 g of 2-(3-butenyl)-2-(4-hydoroxybenzyl)malononitrile,5 ml of N,N-dimethylformamide, 60 mg of sodium hydride (60% in oil), and0.21 g of isopropyl bromide, and according to the process described inthe Production Example 78, there was obtained 227 mg of2-(3-butenyl)-2-(4-isopropoxybenzyl)malononitrile (compound 100).

[0604] Yield: 64%;

[0605]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.34(6H, d), 1.97-2.04(2H, m),2.41-2.52(2H, m), 3.16(2H, s), 4.55(1H, hept), 5.08-5.19(2H, m),5.72-5.89(1H, m), 6.89(2H, d), 7.26(2H, d).

PRODUCTION EXAMPLE 99

[0606] Using 0.72 g of 4-ethylbenzyl chloride, 5 ml ofN,N-dimethylformamide, 0.19 g of sodium hydride (60% in oil), and 0.5 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.48 g of2-allyl-2-(4-ethylbenzyl)malononitrile (compound 101).

[0607] Yield: 57%;

[0608]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.25(3H, t), 2.61-2.74(4H, m),3.18(2H, s), 5.37-5.49(2H, m), 5.88-6.03(1H, m), 7.21-7.33(4H, m).

PRODUCTION EXAMPLE 100

[0609] Using 0.79 g of 4-isopropylbenzyl chloride, 5 ml ofN,N-dimethylformamide, 0.19 g of sodium hydride (60% in oil), and 0.5 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.57 g of2-allyl-2-(4-isopropylbenzyl)malononitrile (compound 102).

[0610] Yield: 62%;

[0611]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.24(6H, d), 2.68(2H, d), 2.91(1H,hept), 3.16(2H, s), 5.38-5.47(2H, m), 5.86-6.00(1H, m), 7.24(2H, d),7.29(2H, d).

PRODUCTION EXAMPLE 101

[0612] Using 0.72 g of (4-(trifluoromethoxy)benzyliden)malononitrile, 20ml of benzene, 1.99 g of allyl tributyl tin, 0.20 g ofazobis(isobutyronitrile) and 2.76 g of 1,1-dimethylethyl iodide, andaccording to the process described in the Production Example 30, therewas obtained 0.20 g of2-allyl-2-(1-(4-(trifluoromethoxy)phenyl)-2,2-dimethylpropyl)malononitrile(compound 103).

[0613] Yield: 61%;

[0614] n_(D) ^(20.5): 1.4762.

PRODUCTION EXAMPLE 102

[0615] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.15 gof 1-bromopentane, and according to the process described in theProduction Example 1, there was obtained 0.12 g of2-pentyl-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 104).

[0616] Yield: 46%;

[0617]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.93(3H, t), 1.34-1.45(4H, m),1.67-1.79(2H, m), 1.94-2.00(2H, m), 3.25(2H, s), 7.51(2H, d), 7.68(2H,d).

PRODUCTION EXAMPLE 103

[0618] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.15 gof 1-bromo-3-methylbutane, and according to the process described in theProduction Example 1, there was obtained 0.14 g of2-(3-methylbutyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound105).

[0619] Yield: 54%;

[0620]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.96(6H, d), 1.57-1.72(3H, m),1.96-2.04(2H, m), 3.25(2H, s), 7.52(2H, d), 7.68(2H, d).

PRODUCTION EXAMPLE 104

[0621] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.15 gof 1-bromo-3-methyl-2-butene, and according to the process described inthe Production Example 1, there was obtained 0.18 g of2-(3-methyl-2-butenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(compound 106).

[0622] Yield: 68%;

[0623]¹H-NMR (CDCl₃, TMS, δ (Ppm)): 1.73(3H, s), 1.85(3H, s), 2.74(2H,d), 3.23(2H, s), 5.34(1H, t), 7.52(2H, d), 7.68(2H, d).

PRODUCTION EXAMPLE 105

[0624] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.14 gof 1-bromo-2-butene, and according to the process described in theProduction Example 1, there was obtained 0.18 g of2-(2-butenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 107).

[0625] Yield: 74%;

[0626]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.74(Z, 3H, dd), 1.81(E, 3H, dd),2.68(E, 2H, d), 2.80(Z, 2H, d), 3.22(E, 2H, s), 3.25(Z, 2H, s),5.52-5.64(1H, m), 5.81-5.95(1H, m), 7.52(2H, d), 7.68(2H, d).

PRODUCTION EXAMPLE 106

[0627] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.14 gof 3-bromo-2-methylpropen, and according to the process described in theProduction Example 1, there was obtained 0.20 g of2-(2-methyl-2-propenyl)-2-(4-(trifluoromethyl)benzyl)malononitrile(compound 108).

[0628] Yield: 71%;

[0629]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.99(3H, s), 2.71(2H, s), 3.27(2H,s), 5.13(1H, d), 5.21(1H, d), 7.54(2H, d), 7.69(2H, d).

PRODUCTION EXAMPLE 107

[0630] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.14 gof 1-bromobutane, and according to the process described in theProduction Example 1, there was obtained 0.16 g of2-butyl-2-(4-(trifluoromethyl)benzyl)malononitrile (compound 109).

[0631] Yield: 57%;

[0632]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.98(3H, t), 1.45(2H, hex),1.67-1.77(2H, m), 1.95-2.01(2H, m), 3.25(2H, s), 7.52(2H, d), 7.68(2H,d).

PRODUCTION EXAMPLE 108

[0633] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.14 gof 1-bromo-2-methylpropane, and according to the process described inthe Production Example 1, there was obtained 0.13 g of2-(2-methylpropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound110).

[0634] Yield: 46%;

[0635]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.13(6H, d), 1.89(2H, d),2.07-2.20(1H, m), 3.25(2H, s), 7.52(2H, d), 7.68(2H, d).

PRODUCTION EXAMPLE 109

[0636] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.15 gof 2-bromobutane, and according to the process described in theProduction Example 1, there was obtained 0.07 g of2-(1-methylpropyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound111).

[0637] Yield: 25%;

[0638]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.07(3H, t), 1.31(3H, d),1.42-1.52(1H, m), 1.91-2.02(2H, m), 3.23(2H, dd), 7.53(2H, d), 7.68(2H,d).

PRODUCTION EXAMPLE 110

[0639] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.15 gof 2-bromopentane, and according to the process described in theProduction Example 1, there was obtained 0.09 g of2-(1-methylbutyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound112).

[0640] Yield: 30%;

[0641]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.01(3H, t), 1.31(3H, d),1.31-1.66(3H, m), 1.72-1.84(1H, m), 2.00-2.10(1H, m), 3.22(2H, dd),7.54(2H, d), 7.68(2H, d).

PRODUCTION EXAMPLE 111

[0642] Using 0.23 g of (4-(trifluoromethyl)benzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.17 gof 2-bromohexane, and according to the process described in theProduction Example 1, there was obtained 0.07 g of2-(1-methylpentyl)-2-(4-(trifluoromethyl)benzyl)malononitrile (compound113).

[0643] Yield: 21%;

[0644]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.95(3H, t), 1.31(3H, d),1.30-1.54(5H, m), 1.79-1.91(1H, m), 1.98-2.07(1H, m), 3.22(2H, dd),7.53(2H, d), 7.68(2H, d).

PRODUCTION EXAMPLE 112

[0645] Using 0.54 g of 2,3-difluorobenzyl bromide, 5 ml ofN,N-dimethylformamide, 0.1 g of sodium hydride (60% in oil), and 0.28 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.31 g of2-allyl-2-(2,3-difluorobenzyl)malononitrile (compound 114).

[0646] Yield: 52%;

[0647]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.74(2H, d), 3.33(2H, s),5.41-5.49(2H, m), 5.88-5.99(1H, m), 7.15-7.26(3H, m).

PRODUCTION EXAMPLE 113

[0648] Using 0.69 g of (4-(2-butyloxy))benzyl bromide, 5 ml ofN,N-dimethylformamide, 0.11 g of sodium hydride (60% in oil), and 0.30 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.31 g of2-allyl-2-(4-(2-butyloxy)benzyl)malononitrile (compound 115).

[0649] Yield: 40%;

[0650]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.97(3H, t), 1.30(3H, d),1.56-1.78(2H, m), 2.70(2H, d), 3.16(2H, s), 4.27-4.35(1H, m),5.39-5.47(2H, m), 5.84-6.01(1H, m), 6.91(2H, d), 7,27(2H, d).

PRODUCTION EXAMPLE 114

[0651] Using 0.80 g of 4-fluoro-3-phenoxybenzyl bromide, 5 ml ofN,N-dimethylformamide, 0.11 g of sodium hydride (60% in oil), and 0.30 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.32 g of2-allyl-2-(4-fluoro-3-phenoxybenzyl)malononitrile (compound 116).

[0652] Yield: 37%;

[0653]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.69(2H, d), 3.10(2H, s),5.37-5.47(2H, m), 5.86-5.97(1H, m), 7.01-7.37(8H, m).

PRODUCTION EXAMPLE 115

[0654] Using 0.70 g of 4-(p-tolylthio)benzyl chloride, 5 ml ofN,N-dimethylformamide, 0.11 g of sodium hydride (60% in oil), and 0.30 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.38 g of2-allyl-2-(4-(p-tolylthio)benzyl)malononitrile (compound 117).

[0655] Yield: 37%;

[0656]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.34(3H, s), 2.69(2H, d), 3.15(2H,s), 5.39-5.48(2H, m), 5.86-5.98(1H, m), 7.23-7.25(8H, m).

PRODUCTION EXAMPLE 116

[0657] Using 0.74 g of 3-phenoxybenzyl bromide, 5 ml ofN,N-dimethylformamide, 0.11 g of sodium hydride (60% in oil), and 0.30 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.54 g of2-allyl-2-(3-phenoxybenzyl)malononitrile (compound 118).

[0658] Yield: 67%;

[0659]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.70(2H, d), 3.15(2H, s),5.37-5.47(2H, m), 5.87-5.98(1H, m)6.91-7.08(6H, m), 7.28-7.37(3H, m).

PRODUCTION EXAMPLE 117

[0660] Using 0.66 g of 4-(m-tolyloxy)benzyl bromide, 5 ml ofN,N-dimethylformamide, 0.11 g of sodium hydride (60% in oil), and 0.30 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.38 g of2-allyl-2-(4-(m-tolyloxy)benzyl)malononitrile (compound 119).

[0661] Yield: 45%;

[0662]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.35(3H, s), 2.71(2H, d), 3.17(2H,s), 5.44(2H, dd), 5.86-6.04(1H, m), 6.81-7.01(4H, m), 7.20-7.35(4H, m).

PRODUCTION EXAMPLE 118

[0663] Using 0.30 g of (2,4,6-trifluorobenzyl)malononitrile, 5 ml ofN,N-dimethylformamide, 0.06 g of sodium hydride (60% in oil), and 0.17 gof allyl bromide, and according to the process described in theProduction Example 1, there was obtained 0.21 g of2-allyl-2-(2,4,6-trifluorobenzyl)malononitrile (compound 120).

[0664] Yield: 59%;

[0665]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.75(2H, d), 3.31(2H, s),5.37-5.46(2H, m), 5.90-6.01(1H, m), 6.81(2H, dd).

PRODUCTION EXAMPLE 119

[0666] Using 0.84 g of 4-(4-chlorophenoxy)benzyl bromide, 5 ml ofN,N-dimethylformamide, 0.11 g of sodium hydride (60% in oil), and 0.30 gof allylmalononitrile, and according to the process described in theProduction Example 93, there was obtained 0.50 g of2-allyl-2-(4-(p-chlorophenoxy)benzyl)malononitrile (compound 121).

[0667] Yield: 55%;

[0668]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.72(2H, d), 3.17(2H, s),5.41-5.49(2H, m), 5.88-6.00(1H, m), 6.96-7.01(4H, m), 7.25-7.36(4H, m).

[0669] The following will describe some production examples forintermediate compounds as reference production examples.

REFERENCE PRODUCTION EXAMPLE 1

[0670] First, 1.00 g of (4-chloro-α-methylbenzylidene)malononitrile ofthe formula:

[0671] was dissolved in 20 ml of diethyl ether, to which a catalyticamount of copper (I) iodide was added, and while stirring under icecooling, a solution of methyl magnesium iodide in diethyl ether(prepared from 0.30 g of magnesium, 10 ml of diethyl ether, and 0.86 mlof methyl iodide) was added dropwise, followed by stirring for 30minutes under ice cooling. Then, 10% hydrochloric acid was added to thereaction mixture, which was extracted with ethyl ether. The organiclayer was successively washed with 10% hydrochloric acid, a saturatedaqueous sodium chloride solution, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to give 0.74 g of(1-(4-chlorophenyl)-1-methylethyl)malononitrile (the intermediate (2)).

[0672] Yield: 69%. REFERENCE PRODUCTION EXAMPLE 2

[0673] First, 1.02 g of (4-chlorobenzylidene)malononitrile was dissolvedin 20 ml of tetrahydrofuran, to which a catalytic amount of copper (I)iodide was added, and while stirring under ice cooling, a solution ofisopropyl magnesium bromide in tetrahydrofuran (prepared from 0.34 g ofmagnesium, 10 ml of tetrahydrofuran, and 1.46 ml of isopropyl bromide)was added dropwise, followed by stirring for 30 minutes under icecooling. Then, 10% hydrochloric acid was added to the reaction mixture,which became acidic and was extracted with ethyl ether. The organiclayer was successively washed with 10% hydrochloric acid, a saturatedaqueous sodium chloride solution, dried over anhydrous magnesiumsulfate, and then concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to give 0.66 g of(1-(4-chlorophenyl)-2-methylpropyl)malononitrile (the intermediate (3)).

[0674] Yield: 52%.

REFERENCE PRODUCTION EXAMPLE 3

[0675] First, 4.44 g of (4-(trifluoromethyl)benzylidene)malononitrilewas dissolved in 20 ml of ethanol, and while stirring at roomtemperature, a suspension of 0.19 g of sodium borohydride in 5 ml ofethanol was added dropwise, followed by stirring at room-temperature for30 minutes. Then, 10% hydrochloride acid was added to the reactionmixture, which became acidic and was extracted with diethyl ether. Theorganic layer was successively washed with 10% hydrochloric acid, asaturated aqueous sodium chloride solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 2.30 gof (4-(trifluoromethyl)benzyl)malononitrile (the intermediate (4)).

[0676] Yield: 51%.

REFERENCE PRODUCTION EXAMPLE 4

[0677] First, 3.00 g of (4-chloro-α-methylbenzylidene)malononitrile wasdissolved in 20 ml of ethanol, and while stirring at room temperature, asuspension of 0.15 g of sodium borohydride in 5 ml of ethanol was addeddropwise, followed by stirring at room temperature for 30 minutes. Then,10% hydrochloride acid was added to the reaction mixture, which wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 1.70 g of (1-(4-chlorophenyl)ethyl)malononitrile(the intermediate (6)).

[0678] Yield: 56%.

REFERENCE PRODUCTION EXAMPLE 5

[0679] First, 10.0 g of 4-(trifluoromethoxy)benzaldehyde and 3.50 g ofmalononitrile were dissolved in 60 ml of 70% (w/w) aqueous ethanol, towhich a catalytic amount of benzyltrimethylammonium hydroxide was added,and the mixture was stirred at room temperature overnight. Then, asaturated aqueous sodium chloride solution was added to the reactionmixture, which was extracted with ethyl acetate. The organic layer waswashed with a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was recrystallized from t-butyl methyl ether andhexane to give 9.24 g of (4-(trifluoromethoxy)benzylidene)malononitrile.

[0680] Yield: 74%;

[0681]¹H-NMR (CDCl₃, TMS, δ (ppm)): 7.37 (2H, d), 7.76 (1H, s), 7.98(2H, d).

[0682] Then, 2.61 g of (4-(trifluoromethoxy)benzylidene)malononitrilewas dissolved in 20 ml of tetrahydrofuran, and while stirring at roomtemperature, a suspension of 0.11 g of sodium borohydride in 5 ml ofethanol was added dropwise, followed by stirring at room temperature for30 minutes. Then, 10% hydrochloric acid was added, and the mixture wasextracted with diethyl ether. The organic layer was successively washedwith 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 2.20 g of(4-(trifluoromethoxy)benzyl)malononitrile (the intermediate (7)).

[0683] Yield: 83%.

REFERENCE PRODUCTION EXAMPLE 6

[0684] Using 1.19 g of (4-(trifluoromethoxy)benzylidene)malononitrile,20 ml of tetrahydrofuran, a catalytic amount of copper (I) iodide, and asolution of isopropyl magnesium bromide in tetrahydrofuran (preparedfrom 0.39 g of magnesium, 10 ml of tetrahydrofuran, and 2.36 g ofisopropyl bromide), and according to the process described in ReferenceProduction Example 2, there was obtained 0.77 g of(1-(4-(trifluoromethoxy)phenyl)-2-methylpropyl)malononitrile (theintermediate (8)).

[0685] Yield: 55%.

REFERENCE PRODUCTION EXAMPLE 7

[0686] Using 1.19 g of (4-(trifluoromethoxy)benzylidene)malononitrile,20 ml of tetrahydrofuran, a catalytic amount of copper (I) iodide, and12.5 ml of a solution of methyl magnesium bromide in tetrahydrofuran(about 1 M, available from Tokyo Kasei Kogyo Co., Ltd), and according tothe process described in Reference Production Example 2, there wasobtained 0.76 g of (1-(4-(trifluoromethoxy)phenyl)ethyl)malononitrile(the intermediate (10)).

[0687] Yield: 60%.

REFERENCE PRODUCTION EXAMPLE 8

[0688] First, 4.46 g of (3,4-dichlorobenzylidene)malononitrile wasdissolved in 20 ml of tetrahydrofuran, and while stirring at roomtemperature, a suspension of 0.19 g of sodium borohydride in 5 ml ofethanol was added drop-wise, followed by stirring at room temperaturefor 30 minutes. Then, 10% hydrochloride acid was added and the mixturewas extracted with diethyl ether. The organic layer was successivelywashed with 10% hydrochloric acid, a saturated aqueous sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to give 3.15 g of (3,4-dichlorobenzyl)malononitrile (theintermediate (12)).

[0689] Yield: 70%.

REFERENCE PRODUCTION EXAMPLE 9

[0690] Using 4.46 g of (2,4-dichlorobenzylidene)malononitrile, 20 ml oftetrahydrofuran, and a suspension of 0.19 g of sodium borohydride in 5ml of ethanol, and according to the process described in ReferenceProduction Example 8, there was obtained 3.10 g of(2,4-dichlorobenzyl)malononitrile (the intermediate (13)).

[0691] Yield: 69%.

REFERENCE PRODUCTION EXAMPLE 10

[0692] First, 10.0 g of 4-(trifluoromethylthio)benzaldehyde and 2.92 gof malononitrile were dissolved in 50 ml of 70% (w/w) aqueous ethanol,to which a catalytic amount of benzyltrimethylammonium hydroxide wasadded, and the mixture was stirred at room temperature overnight. Then,a saturated aqueous sodium chloride solution was added to the reactionmixture, which was extracted with ethyl acetate. The organic layer waswashed with a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was recrystallized with a solvent systemconsisting of t-butyl methyl ether and hexane to give 10.5 g of(4-(trifluoromethylthio)benzylidene)malononitrile.

[0693] Yield: 85%;

[0694]¹H-NMR (CDCl₃, TMS, δ (ppm)): 7.78 (1H, s), 7.79 (2H, d), 7.93(2H, d).

[0695] Then, 8.00 g of (4-(trifluoromethylthio)benzylidene)malononitrileand 3.35 g of benzaldehyde were dissolved in 320 ml of ethanol, andwhile stirring at room temperature, 3.41g of phenylenediamine was slowlyadded, and the mixture was stirred at room temperature for 5 hours.Then, the reaction mixture was concentrated, 300 ml of t-butyl methylether was added, and insoluble matters were filtered. The filtrate wasconcentrated and the resulting residue was subjected to silica gelchromatography to give 6.22 g of(4-(trifluoromethylthio)benzyl)malononitrile (the intermediate (14)).

[0696] Yield: 77%.

REFERENCE PRODUCTION EXAMPLE 11

[0697] First, 9.78 g of malononitrile, 954 mg of tetrabutylammoniumbromide, and 10.0 g of 4-bromo-1-butene were mixed, and while stirringat 0° C. under an atmosphere of nitrogen, 8.3 g of potassium t-butoxidewas slowly added. The mixture was further stirred at room temperaturefor 12 hours. Then, the reaction mixture was poured into water, followedby extraction with t-butyl methyl ether. The organic layer was washedwith water, a saturated aqueous sodium chloride solution, dried overanhydrous magnesium sulfate, and then concentrated under reducedpressure. The residue was subjected to silica gel column chromatographyto give 2.31 g of (3-butenyl)malononitrile (the intermediate (16)).

[0698] Yield: 26%.

REFERENCE PRODUCTION EXAMPLE 12

[0699] Using 4.00 g of (4-(trifluoromethoxy)benzylidene)malononitrile,30 ml of tetrahydrofuran, 175 mg of copper (I) bromide dimethyl sulfidecomplex, and 26 ml of a solution (0.98 M) of vinyl magnesium bromide intetrahydrofuran, and according to the process described in ReferenceProduction Example 2, there was obtained 1.60 g of(1-(4-trifluoromethoxyphenyl))-2-propenylmalononitrile (the intermediate(18)).

REFERENCE PRODUCTION EXAMPLE 13

[0700] Using 5.00 g of (2-methoxybenzylidene)malononitrile, 40 ml oftetrahydrofuran, and a suspension of 0.31 g of sodium borohydride in 10ml of ethanol, and according to the process described in ReferenceProduction Example 8, there was obtained 3.56 g of(2-methoxybenzyl)malononitrile (the intermediate (20)).

[0701] Yield: 70%.

REFERENCE PRODUCTION EXAMPLE 14

[0702] First, 9.18 g of (4-hydroxybenzyl)malononitrile was dissolved in90 ml of N,N-dimethylformamide, to which 2.56 g of sodium hydride (60%in oil) was added, while stirring under ice cooling. After the evolutionof hydrogen gas ceased, while stirring under ice cooling, 7.21 g of4-bromo-1-betene was added dropwise, followed by further stirring atroom temperature overnight. Then, a saturated aqueous ammonium chloridesolution was added to the reaction mixture, which was extracted withdiethyl ether. The organic layer was successively washed with water, asaturated aqueous sodium chloride solution, dried over anhydrousmagnesium sulfate, and then concentrated under reduced pressure. Theresidue was subjected to silica gel column chromatography to give 10.3 gof 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrile (the intermediate(23)).

[0703] Yield: 86%.

REFERENCE PRODUCTION EXAMPLE 15

[0704] Using 5.23 g of (4-ethoxybenzylidene)malononitrile, 40 ml oftetrahydrofuran, and a suspension of 0.35 g of sodium borohydride in 10ml of ethanol, and according to the process described in ReferenceProduction Example 8, there was obtained 2.76 g of(4-ethoxybenzyl)malononitrile (the intermediate (25)).

[0705] Yield: 52%.

REFERENCE PRODUCTION EXAMPLE 16

[0706] Using 3.00 g of (3-chloro-α-methylbenzylidene)malononitrile ofthe formula:

[0707] 60 ml of diethyl ether, a catalytic amount of copper (I) iodide,and methyl magnesium iodide in diethyl ether (prepared from 0.90 g ofmagnesium, 30 ml of diethyl ether, and 2.58 ml of methyl iodide), andaccording to the process described in Reference Production Example 1,there was obtained 2.33 g of(1-(3-chlorophenyl)-1-methylethyl)malononitrile (the intermediate (26)).

[0708] Yield: 73%.

REFERENCE PRODUCTION EXAMPLE 17

[0709] Using 3.00 g of (2-chloro-α-methylbenzylidene)malononitrile ofthe formula:

[0710] 60 ml of diethyl ether, a catalytic amount of copper (I) iodide,and methyl magnesium iodide in diethyl ether (prepared from 0.90 g ofmagnesium, 30 ml of diethyl ether, and 2.58 ml of methyl iodide), andaccording to the process described in Reference Production Example 1,there was obtained 1.16 g of(1-(2-chlorophenyl)-1-methylethyl)malononitrile (the intermediate (27)).

[0711] Yield: 36%.

REFERENCE PRODUCTION EXAMPLE 18

[0712] Using 4.46 g of (2,3-dichlorobenzylidene)malononitrile, 20 ml oftetrahydrofuran, and a suspension of 0.21 g of sodium borohydride in 5ml of ethanol, and according to the process described in ReferenceProduction Example 8, there was obtained 3.07 g of(2,3-dichlorobenzyl)malononitrile (the intermediate (29)).

[0713] Yield: 68%.

REFERENCE PRODUCTION EXAMPLE 19

[0714] Using 4.46 g of (2,6-dichlorobenzylidene)malononitrile, 20 ml oftetrahydrofuran, and a suspension of 0.21 g of sodium borohydride in 5ml of ethanol, and according to the process described in ReferenceProduction Example 8, there was obtained 2.73 g of(2,6-dichlorobenzyl)malononitrile (the intermediate (30)).

[0715] Yield: 61%.

REFERENCE PRODUCTION EXAMPLE 20

[0716] Using 4.88 g of (2,3,4,5,6-pentafluorobenzylidene)malononitrile,20 ml of tetrahydrofuran, and a suspension of 0.21 g of sodiumborohydride in 5 ml of ethanol, and according to the process describedin Reference Production Example 8, there was obtained 2.20 g of(2,3,4,5,6-pentafluorobenzyl)malononitrile (the intermediate (31)).

[0717] Yield: 45%.

REFERENCE PRODUCTION EXAMPLE 21

[0718] Using 1.02 g of (3-chlorobenzylidene)malononitrile, 20 ml oftetrahydrofuran, a catalytic amount of copper (I) iodide, and 10 ml ofisopropyl magnesium bromide in tetrahydrofuran (1.4 M), and according tothe process described in Reference Production Example 2, there wasobtained 0.71 g of (1-(3-chlorophenyl)-2-methylpropyl)malononitrile (theintermediate (32)).

[0719] Yield: 56%.

REFERENCE PRODUCTION EXAMPLE 22

[0720] First, 13.2 g of (2,2-dimethylpropylidene)malononitrile and 10.5g of benzaldehyde was dissolved in 800 ml of ethanol, to which 10.6 g of1,2-phenylenediamine was added slowly while stirring, followed bystirring overnight at room temperature. Then, the reaction mixture wasconcentrated under reduced pressure. Then, 300 ml of chloroform wasadded to the residue, the precipitate was filtered off, the filtrate wasconcentrated. And the same operation was repeated once more. The residuewas subjected to silica gel column chromatography to give 8.50 g of(2,2-dimethylpropyl)malononitrile (the intermediate (34)).

[0721] Yield: 64%.

[0722] The intermediate compounds used in the production of thecompounds are shown below with the compound numbers and physical data.

[0723] Intermediate (1)

[0724] (4-Chlorobenzyl)malononitrile

[0725] m.p.: 96.9° C.

[0726] Intermediate (2)

[0727] (1-(4-Chlorophenyl)-1-methylethyl)malononitrile

[0728] n_(D) ^(22.0): 1.5372.

[0729] Intermediate (3)

[0730] (1-(4-Chlorophenyl)-2-methylpropyl)malononitrile

[0731] n_(D) ^(21.5): 1.5289.

[0732] Intermediate (4)

[0733] (4-(Trifluoromethyl)benzyl)malononitrile

[0734] m.p.: 79.1° C.

[0735] Intermediate (5)

[0736] (4-Cyanobenzyl)malononitrile

[0737] m.p.: 118.7° C.

[0738] Intermediate (6)

[0739] (1-(4-Chlorophenyl)ethyl)malononitrile

[0740] n_(D) ^(24.5): 1.5349.

[0741] Intermediate (7)

[0742] (4-(Trifluoromethoxy)benzyl)malononitrile

[0743] m.p.: 88.3° C.

[0744] Intermediate (8)

[0745] (1-(4-(Trifluoromethoxy)phenyl-2-methylpropyl)malononitrile

[0746]¹H-NMR (CDCl₃, TMS, δ (ppm)): 0.83 (3H, d), 1.16 (3H, d),2.29-2.45 (1H, m), 2.87 (1H, dd), 4.18 (1H, d), 7.25-7.30 (2H, m),7.38-7.42 (2H, m).

[0747] Intermediate (9)

[0748] (4-Bromobenzyl)malononitrile

[0749] m.p.: 97.7° C.

[0750] Intermediate (10)

[0751] (1-(4-(Trifluoromethoxy)phenyl)ethyl)malononitrile

[0752]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.65 (3H, d), 3.49 (1H, dq), 3.85(1H, d), 7.24-7.29 (2H, m), 7.38-7.42 (2H, m).

[0753] Intermediate (11)

[0754] (4-Fluorobenzyl)malononitrile

[0755] m.p.: 117.2° C.

[0756] Intermediate (12)

[0757] (3,4-Dichlorobenzyl)malononitrile

[0758] m.p.: 83.3° C.

[0759] Intermediate (13)

[0760] (2,4-Dichlorobenzyl)malononitrile

[0761] m.p.: 62.5° C.

[0762] Intermediate (14)

[0763] (4-(Trifluoromethylthio)benzyl)malononitrile

[0764]¹H-NMR (CDCl₃, TMS, δ (ppm)): 3.15 (2H, d), 3.95 (1H, t), 7.37(2H, d), 7.70 (2H, d).

[0765] Intermediate (15)

[0766] Allylmalononitrile

[0767]¹H-NMR (CDCl₁₃, TMS, δ (ppm)): 2.75 (2H, dd), 3.79 (1H, t),5.36-5.45 (2H, m), 5.75-5.94 (1H, m).

[0768] Intermediate (16)

[0769] (3-Butenyl)malononitrile

[0770]¹H-NMR (CDCl₃, TMS, δ (ppm)): 2.11-2.18(2H, m), 2.31-2.41 (2H, m),3.76 (1H, t), 5.16-5.26 (2H, m), 5.64-5.79 (1H, m).

[0771] Intermediate (17)

[0772] (2-chlorobenzyl)malononitrile

[0773] n_(D) ^(19.5): 1.5384.

[0774] Intermediate (18)

[0775] (1-(4-Trifluoromethoxyphenyl)-2-propenyl)malononitrile

[0776]¹H-NMR (CDCl₃, TMS, δ (ppm)): 3.95-4.03 (2H, m), 5.40-5.53 (2H,m), 6.08-6.19 (1H, m), 7.28 (2H, d), 7.39 (2H, d).

[0777] Intermediate (19)

[0778] (3-chlorobenzyl)malononitrile

[0779] n_(D) ^(19.5):1.5403.

[0780] Intermediate (20)

[0781] (2-methoxybenzyl)malononitrile

[0782] n_(D) ^(19.5): 1.5248.

[0783] Intermediate (21)

[0784] (3-methoxybenzyl)malononitrile

[0785] m.p.: 55.5° C.

[0786] Intermediate (22)

[0787] (4-methoxybenzyl)malononitrile

[0788] m.p.: 89.6° C.

[0789] Intermediate (23)

[0790] 2-(3-butenyl)-2-(4-hydroxybenzyl)malononitrile

[0791]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.99-2.05(2H, m), 2.43-2.51(2H, m),3.16(2H, s), 4.99(1H, bs), 5.09-5.20(2H, m), 5.74-5.86(1H, m), 6.85(2H,d), 7.24(2H, d).

[0792] Intermediate (24)

[0793] (3,4-(methylenedioxy)benzyl)malononitrile

[0794]¹H-NMR (CDCl₃, TMS, δ (ppm)): 3.19(2H, d), 3.87(1H, t), 5.98(2H,s), 6.73-6.83(3H, m).

[0795] Intermediate (25)

[0796] (4-ethoxybenzyl)malononitrile

[0797] m.p.: 118.0° C.

[0798] Intermediate (26)

[0799] (1-(3-chlorophenyl)-1-methylethyl)malononitrile

[0800] n_(D) ^(22.5): 1.5376.

[0801] Intermediate (27)

[0802] (1-(2-chlorophenyl)-1-methylethyl)malononitrile

[0803] m.p.: 90.2° C.

[0804] Intermediate (28)

[0805] (4-nitrobenzyl)malononitrile

[0806] m.p.: 155.7° C.

[0807] Intermediate (29)

[0808] (2,3-dichlorobenzyl)malononitrile

[0809] n_(D) ^(22.5): 1.5518.

[0810] Intermediate (30)

[0811] (2,6-dichlorobenzyl)malononitrile

[0812] m.p.: 87.7° C.

[0813] Intermediate (31)

[0814] (2,3,4,5,6-pentafluorobenzyl)malononitrile

[0815] m.p.: 96.3° C.

[0816] Intermediate (32)

[0817] (1-(3-chlorophenyl)-2-methylprpyl)malononitrile

[0818] n_(D) ^(21.5): 1.5268.

[0819] Intermediate (33)

[0820] (4-methylbenzyl)malononitrile

[0821] m.p.: 83.7° C.

[0822] Intermediate (34)

[0823] (2,2-dimethylpropyl)malononitrile

[0824]¹H-NMR (CDCl₃, TMS, δ (ppm)): 1.07(9H, s), 2.04(2H, d), 3.66(1H,t).

[0825] Intermediate (35)

[0826] (3-(trifluoromethoxy)benzyl)malononitrile

[0827]¹H-NMR (CDCl₃, TMS, δ (ppm)): 3.34(2H, d), 3.97(1H, t),7.25-7.50(4H, m).

[0828] Specific examples of the compounds (X) are shown in Table 1 withtheir compound numbers. TABLE 1 The compounds of formula (X):

(X) No. R¹ R² R³ R⁴ (R⁵)_(m) R⁶ 1 H H H CH═CH₂ — Cl 2 CH₃ CH₃ H CH═CH₂ —Cl 3 H CH(CH₃)₂ H CH═CH₂ — Cl 4 H H H CH₂CH═CH₂ — Cl 5 H H H CH═CH₂ —CF₃ 6 H H H CH₂CH═CH₂ — CN 7 H H H (CH₂)₂CH═CH₂ — CN 8 H H H CH═CH₂ 2-ClH 9 H H CH₂CH₂CH₂CH₂CH₂ — Cl 10 H CH₃ H CH₂CH═CH₂ — Cl 11 H H H CH═CH₂ —OCF₃ 12 H CH(CH₃)₂ H CH₂CH═CH₂ — OCF₃ 13 H H H CHCH₂ — Br 14 H H HCH═CH₂ — CN 15 H H H CH₂CH═CH₂ — OCF₃ 16 H CH₃ H CH₂CH═CH₂ — OCF₃ 17 H HH CH═CH₂ 3-Cl H 18 H H H CH═CH₂ — F 19 H H H CH(CH₃)₂ — Cl 20 H H HCH═CH₂ 2-OCH₃ H 21 H H H (CH₂)₂CH═CH₂ — Cl 22 H H CH₃ CH═CH₂ — Cl 23 H HH CH═CH₂ 3-Cl Cl 24 H H H CH═CH₂ 2-Cl Cl 25 H H H CH═C(CH₃)₂ — Cl 26 HCH(CH₃)₂ H CH₂CH═CH₂ — Cl 27 H H H CH═C(CH₃)₂ — OCF₃ 28 H H H CH═CH₂3-OCH₃ H 29 H H H CH═CH₂ — OCH₃ 30 H CH₃ H CH═CH₂ — OCF₃ 31 H CH₂Cl HCH═CH₂ — OCF₃ 32 H CH═CH₂ H CH₂CH═CH₂ — OCF₃ 33 H CH═CH₂ H CH═CH₂ — OCF₃34 H CH═CH₂ H C≡CH — OCF₃ 35 H H H CH₂CHCH₂ — OCBrF₂ 36 H H H CH₂CH═CH₂— OCHF₂ 37 H H H CH₂CH═CH₂ — 3,4-OCH₂O 38 H H H CH₂CH═CH₂ — OCH₂CH═CH₂39 H OCH₃ H CH═CH₂ — OCF₃ 40 H OCH₂CF₃ H CH═CH₂ — OCF₃ 41 H H H CH═CH₂ —SCF₃ 42 H H H CH₂CH═CH₂ — SCF₃ 43 H OCH₃ H CH═CH₂ — SCF₃ 44 H H H CH═CH₂— OCH₂CH₃ 45 H H H CH₂CH(CH₃)₂ — OCF₃ 46 H H H CH═CHCH₃ — SCF₃ 47 H HCH₃ CH═CH₂ — SCF₃ 48 CH₃ CH₃ H CH═CH₂ 3-Cl H 49 CH₃ CH₃ H CH═CH₂ 2-Cl H50 H H H CH═CH₂ — NO₂ 51 H H CH₃ CH₃ — Cl 52 H H H CH₂CH═CH₂ — CF₃ 53 HH H CH═CH₂ 2,3-Cl₂ — 54 H H H CH═CH₂ 2,6-Cl₂ 55 H CN H CH═CH₂ — OCF₃ 56H CN H CH═CH₂ — SCF₃ 57 H H H CH═CH₂ 2-CF₃ CF₃ 58 H H H CH═CH₂ 2-Cl CF₃59 H H H C≡CCH₃ — OCF₃ 60 H H H CH₂CH-CH₂ 2-Cl CF₃ 61 H H H CH═CH₂ —S(O)2CH₃ 62 H H H CH═CH₂ 2,3,5,6-F₄ F 63 H H H CH═CH₂ 2-NO₂ CF₃ 64 H H HCH═CH₂ 2,6-Cl₂ CF₃ 65 H H H CH₂CH═CH₂ 2,6-Cl₂ CF₃ 66 H CH(CH₃)₂ H CH═CH₂3-Cl H 67 H H H CH₂CH═CH₂ 2-NO₂ CF₃ 68 H H H H — Cl 69 H H H CH═CH₂ 3-FCF₃ 70 H H H CH═CH₂ — SCH₃ 71 H H H C₂H₅ — CF₃ 72 H H H CH₃ — Cl 73 H HH (Z)-CH₂CH═CHCH₂CH₃ — Cl 74 H CH₃ H CH═CH₂ — Cl 75 H H H CH₃ — CF₃ 76 HCH₃ H CH₂CH₂CH═CH₂ — Cl 77 H H H CH═CH₂ — — CH₃ 78 H H H CH₂CH═CH₂ —OC(═O)CH₃ 79 H H H (CH₂)₂CH═CH₂ — CF₃ 80 H H H CH₂CH═CH₂ — OCF₂CF₂H 81 HH H CH₂CH═CH₂ — OCH₂CF₃ 82 H OCH₂CH₃ H CH═CH₂ — OCF₃ 83 H OCH₃ H CH═CH₂— CN 84 H OCH₃ H CH═CH₂ — Cl 85 H H H C(CH₃)₃ — OCF₃ 86 H H H C(CH₃)₃ —Br 87 H H H CH(CH₃)₂ — OCF₃ 88 H H H CH₂CH₂CH₂CH₃ — OCF₃ 89 H H H CH═CH₂3-OCF₃ H 90 H H H CH₂CH═CH₂ 3-OCF₃ H 91 H CN H CH═CH₂ — OCH₃ 92 H CN HCH═CH₂ — CH₃ 93 H CN H CH═CH₂ — C(═O)OCH₃ 94 H H H CH₂CH═CH₂ 3,5-(CF₃)₂H 95 H H H CH═CH₂ 2,3-(OCH₃)₂ H 96 H H H CH═CH₂ — CH═CH₂ 97 H H H CH═CH₂— C(═O)CH₃ 98 H H H CH₂CH═CH₂ — OCH₂CH₃ 99 H H H CH₂CH═CH₂ OCH₂CH₂CH₃100 H H H CH₂CH═CH₂ — OCH(CH₃)₂ 101 H H H CH═CH₂ — CH₂CH₃ 102 H H HCH═CH₂ — CH(CH₃)₂ 103 H C(CH₃)₃ H CH═CH₂ — OCF₃ 104 H H H CH₂CH₂CH₂CH₃ —CF₃ 105 H H H CH₂CH(CH₃)₂ — CF₃ 106 H H H CH═C(CH₃)₂ — CF₃ 107 H H HCH═CHCH₃ — CF₃ 108 H H H C(CH₃)═CH₂ — CF₃ 109 H H H CH₂CH₂CH₃ — CF₃ 110H H H CH(CH₃)₂ — CF₃ 111 H H CH₃ CH₂CH₃ — CF₃ 112 H H CH₃ CH₂CH₂CH₃ —CF₃ 113 H H CH₃ CH₂CH₂CH₂CH₃ — CF₃ 114 H H H CH═CH₂ 2,3-F₂ H 115 H H HCH═CH₂ — OCH(CH₃)CH₂CH₃ 116 H H H CH═CH₂ 3-OPh F 117 H H H CH═CH₂ —S(p-CH₃Ph) 118 H H H CH═CH₂ 3-OPh H 119 H H H CH═CH₂ — O(m-CH₃Ph) 120 HH H CH═CH₂ 2,6-F₂ F 121 H H H CH═CH₂ — O(p-ClPh) 122 H H H CH₂CH(CH₃)₂3-Cl Cl 123 H H H CH₂CH(CH₃)₂ — Cl 124 H H H CH₂CH(CH₃)₂ — CN 125 H H HCH₂CH(CH₃)₂ — NO₂ 126 H H H CH₂CH(CH₃)₂ 3-F CF₃ 127 H H H CH₂CH(CH₃)₂3-Cl CN 128 H CH₃ H CH₂CH(CH₃)₂ — CF₃ 129 H CH₃ H CH₂CH(CH₃)₂ — Cl 130 HCH₃ H CH₂CH(CH₃)₂ — CN 131 H CH(CH₃)₂ H CH₂CH(CH₃)₂ — CF₃ 132 H H HCH₂CH(CH₃)₂ 3-CF₃ H 133 H H H CH₂CH(CH₃)₂ — CF₃ 134 CH₃ CH₃ HCH₂CH(CH₃)₂ — CN 135 CH₃ CH₃ H CH₂CH(CH₃)₂ 3-Cl Cl 136 H H H CH₂C(CH₃)₃— CF₃ 137 H H H CH₂C(CH₃)₃ — Cl 138 H H H CH₂C(CH₃)₃ — CN 139 H H HCH₂C(CH₃)₃ — NO₂ 140 H H H CH₂C(CH₃)₃ 3-Cl CF₃ 141 H H H CH₂C(CH₃)₃ 3-FCN 142 H CH₃ H CH₂C(CH₃)₃ — CF₃ 143 H CH₃ H CH₂C(CH₃)₃ 3-F CF₃ 144 HCH(CH₃)₂ H CH₂C(CH₃)₃ 3-F CF₃ 145 H CH(CH₃)₂ H CH₂C(CH₃)₃ — CF₃ 146 H HH CH₂C(CH₃)₃ 3-F Cl 147 H H H CH₂C(CH₃)₃ 3-Cl F 148 H H H CH═CH₂ 3-ClCF₃ 149 H CH₃ H CH═CH₂ 3-F CF₃ 150 H H H CH═CH₂ 3-CF₃ H 151 H H H CH═CH₂3-Cl CN 152 H H H CH₂CH═CH₂ 3-Cl CF₃ 153 H H H CH₂CH═CH₂ 3-F CF₃ 154 H HH CH₂CH═CH₂ 3-F CN 155 H H H CH₂CH═CH₂ 3-Cl F 156 H CH₃ H CH₂CH═CH₂ 3-FCl 157 H CH₃ H CH═C(CH₃)₂ 3-F Cl 158 H H H CH═C(CH₃)₂ 3-Cl CF₃ 159 H H HCH═C(CH₃)₂ 3-F CF₃ 160 H CH(CH₃)₂ H CH═C(CH₃)₂ — CF₃ 161 H H HCH═C(CH₃)₂ 3-CF₃ H 162 H H H CH₂CH═C(CH₃)₂ — CF₃ 163 H H H CH₂CH═C(CH₃)₂— CN 164 H H H CH₂CH═C(CH₃)₂ — NO₂ 165 H H H CH₂CH₃ 3-F CF₃ 166 H H HCH₂CH₃ — CN 167 H H H CH₂CH₃ — Cl 168 H H H CH₂CH₃ — NO₂ 169 H CH₃ HCH₂CH₃ — CF₃ 170 H CH₃ H CH₂CH₃ — CN 171 H H H CH₂CH₂CH₃ 3-F Cl 172 H HH CH₂CH₂CH₃ 3-Cl F 173 H H H CH₂CH₂CH₃ 3-F CF₃ 174 H CH₃ H CH₂CH₂CH₃3-CF₃ H 175 H H H CH₂CH₃ 3-CF₃ H 176 H H H CH₂CH₂CH₃ 3-CF₃ H 177 H CH₂FH CH₂CH═CH₂ — CF₃ 178 H H H CH₂CH₂CH₃ — SCF₃ 179 H H H CH₂CH₃ — OCF₃ 180H CF₃ H CH₂CH₃ 3-F CF₃

[0829] The following will describe some formulation examples whereinparts represent parts by weight. The compounds (X) are designated bytheir compound numbers shown in Table 1.

FORMULATION EXAMPLE 1

[0830] Nine (9) parts of each of compounds 1 to 120 is dissolved in 37.5parts of xylene and 37.5 parts of dimethylformamide, and 10 parts ofpolyoxyethylene styryl phenyl ether and 6 parts of calciumdodecylbenzenesulfonate are added thereto, followed by well stirring andmixing, to give an emulsifiable concentrate for each compound.

FORMULATION EXAMPLE 2

[0831] To 40 parts of each of compounds 1 to 120 is added 5 parts ofSorpol® 5060 (Toho Chemical Industry Co., Ltd.), followed by wellmixing, and 32 parts of Carplex® #80 (synthetic hydrated silicone oxidefine powder; Shionogi & Co., Ltd.) and 23 parts of 300 mesh diatomaceousearth are added, which is mixed with a mixer to give a wettable powderfor each compound.

FORMULATION EXAMPLE 3

[0832] To 3 parts of each of compounds 1 to 120 are added 5 parts ofsynthetic hydrated silicon oxide fine powder, 5 parts of sodiumdodecylbenzenesulfonate, 30 parts of bentonite, and 57 parts of clay,followed by well stirring and mixing, and an appropriate amount of wateris added to this mixture, followed by further stirring, granulation witha granulator, and air drying, to give a granule for each compound.

FORMULATION EXAMPLE 4

[0833] First, 4.5 parts of each of compounds 1 to 120, 1 part ofsynthetic hydrated silicon oxide fine powder, 1 part of Doriresu B(Sankyo Co., Ltd.) as a flocculant, and 7 parts of clay are well mixedwith a mortar, followed by stirring and mixing with a mixer. To theresulting mixture is added 86.5 parts of cut clay, followed by wellstirring and mixing, to give a dust for each compound.

FORMULATION EXAMPLE 5

[0834] Ten parts of each of compounds 1 to 120, 35 parts of white carboncontaining 50 parts of polyoxyethylene alkyl ether sulfate ammoniumsalt, and 55 parts of water are mixed and pulverized by the wet grindingmethod to give a formulation for each compound.

FORMULATION EXAMPLE 6

[0835] First, 0.5 parts of each of compounds 1 to 120 is dissolved in 10parts of dichloromethane, which is mixed with 89.5 parts of ISOPAR® M(isoparaffin; Exxon Chemical Co.) to give an oil formulation for eachcompound.

FORMULATION EXAMPLE 7

[0836] First, 0.1 parts of compounds 1 to 120 and 49.9 parts ofNEO-CHIOZOL (Chuo Kasei K. K.) are put into an aerosol can, to which anaerosol valve is attached. Then, 25 parts of dimethyl ether and 25 partsof LPG are filled in the aerosol can, followed by shaking and attachmentof an actuator, to give an oil-based aerosol.

FORMULATION EXAMPLE 8

[0837] First, 0.6 parts of each of compounds 1 to 120, 0.01 parts ofBHT, 5 parts of xylene, 3.39 parts of deodorized kerosine, and 1 part ofan emulsifier (Atmos 300; Atmos Chemical Co.) are mixed to become asolution. Then, this solution and 50 parts of distilled water are filledin an aerosol can, to which a valve part is attached, and 40 parts of apropellant (LPG) is filled under pressure through the valve in theaerosol can to give a water-based aerosol.

[0838] The following test example will demonstrate that the compounds(X) are useful as the active ingredients of pesticide compositions. Thecompounds (X) are designated by their compound numbers shown in Table 1.

TEST EXAMPLE 1 Pesticidal Test Against Nilaparvata Lugens

[0839] Each formulation of the compound 11, 12, 16, 27, 30, 31, 32, 33,34, 37, 40, 41, 42, 47, 49, 52, 56, 58, 59, 60, 63, 64, 65, 67, 69, 71,75, 79, 87, 88, 89, 90, 98, 100, 102, 105, 106, 108, 109, 110, 114, 115,116, 117, 118 and 119 obtained according to Formulation Example 5 wasdiluted with water so that the active ingredient concentration came to500 ppm to prepare a test liquid for each compound.

[0840] Fifty grams of molding Bonsoru 2 (available from SumitomoChemical Co., Ltd.) was put into a polyethylene cup, and 10 to 15 seedsof rice were planted in the polyethylene cup. Then rice plants weregrown until the second foliage leaves developed and then cut into thesame height of 5 cm. The test liquid, which had been prepared asdescribed above, was sprayed at the rate of 20 ml/cup onto these riceplants. After the test liquid sprayed onto the rice plants were dried,the polyethylene cup with the rice plants was placed in a largepolyethylene cup and 30 first-instar larvae of Nilaparvata lugens (brownplanthopper) were set free in the large polyethylene cup, which was thenkept covered and left in a greenhouse at 25° C. On the 6th day after therelease of larvae of Nilaparvata lugens, the number of parasiticNilaparvata lugens on the rice plants was examined.

[0841] As a result, in the treatment with each of the compoundsdescribed above, the number of parasitic pests on the 6th day after thetreatment was not greater than 3.

TEST EXAMPLE 2 Pesticidal Test against Nilaparvata Lugens

[0842] Each formulation of the compound 11, 12, 16, 41, 45, 47, 49, 52,54, 58, 68, 69, 71, 75, 87, 90, 105, 106, 108, 109 and 110 obtainedaccording to Formulation Example 5 was diluted with water so that theactive ingredient concentration came to 45.5 ppm to prepare a testliquid for each compound.

[0843] Fifty grams of molding Bonsoru 2 (available from SumitomoChemical Co., Ltd.) was put into a polyethylene cup having five holes of5 mm, and 10 to 15 seeds of rice were planted in the polyethylene cup.Then rice plants were grown until the second foliage leaves developedand the polyethylene cup with the rice plants was placed in a largepolyethylene cup containing 55 ml of the test liquid, which had beenprepared as described above. The rice plants were left in a greenhouseat 25° C. for 6 days and then cut into the same height of 5 cm. Thirtyfirst-instar larvae of Nilaparvata lugens (brown planthoppers) were setfree in the large polyethylene cup, which was then kept covered and leftin a greenhouse at 25° C. On the 6th day after the release of larvae ofNilaparvata lugens, the number of parasitic Nilaparvata lugens on therice plants was examined.

[0844] As a result, in the treatment with each of the compoundsdescribed above, the number of parasitic pests on the 6th day after thetreatment was not greater than 3.

TEST EXAMPLE 3 Pesticidal Test Against Nilaparvata lugens

[0845] Each formulation of the compound 1, 2, 3, 4, 5, 6, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 25, 26, 27, 29, 44, 48,49, 51, 62, 66, 73, 74, 76 and 77 obtained according to FormulationExample 1 was diluted with water so that the active ingredientconcentration came to 500 ppm to prepare a test liquid for eachcompound.

[0846] A bundle of 3 to 4 of cotyledons (height of 3 to 5 cm) of ricewas immersed in the test liquid, which had been prepared as describedabove, for 1 minute. After the test liquid treated the rice plants wasdried, a filter paper moistened with 1 ml of water was place on a bottomof polyethylene cup and then the bundle of cotyledons of rice was placedon it. Thirty first-instar larvae of Nilaparvata lugens (brownplanthoppers) were set free in the polyethylene cup, which was then keptcovered and left in a greenhouse at 25° C. On the 6th day after therelease of larvae of Nilaparvata lugens, the number of parasiticNilaparvata lugens on the rice plants was examined.

[0847] As a result, in the treatment with each of the compoundsdescribed above, the number of parasitic pests on the 6th day after thetreatment was not greater than 3.

TEST EXAMPLE 4 Pesticidal Test Against Diabrotica undecimpunctata

[0848] Each formulation of the compound 1, 2, 3, 4, 5, 9, 10, 11, 12,16, 19, 21, 22, 23, 24, 26, 66, 74 and 76 obtained according toFormulation Example 1 was diluted with water so that the activeingredient concentration came to 50 ppm to prepare a test liquid foreach compound.

[0849] On the bottom of a polyethylene cup of 5 cm in diameter wasplaced a filter paper, to which the test liquid had been prepared asdescribed above, was added dropwise in an amount of 1 ml. One germinatedseed of corn and 30 to 50 eggs of Diabrotica undecimpunctata(southern-corn rootworm) was placed on the filter paper in thepolyethylene cup, which was then kept covered and left in a room at 25°C. On the 6th day after, the number of surviving larvae of Diabroticaundecimpunctata was examined.

[0850] As a result, in the treatment with each of the compoundsdescribed above, the number of surviving pests on the 6th day after was0.

TEST EXAMPLE 5 Pesticidal Test Against Musca domestics

[0851] Each formulation of the compound 1, 3, 4, 10, 11, 15, 17, 22, 24,30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 45, 46, 47, 52, 55,56, 57, 58, 59, 60, 64, 65, 66, 67, 68, 69, 71, 74, 75, 79, 82, 84, 89,90, 92, 101, 102, 105, 107, 108, 109, 110, 111, 114, 115 and 120obtained according to Formulation Example 5 was diluted with water sothat the active ingredient concentration came to 500 ppm to prepare atest liquid for each compound.

[0852] On the bottom of a polyethylene cup of 5.5 cm in diameter wasplaced a filter paper on the same size, to which the test liquid hadbeen prepared as described above, was added dropwise in an amount of 0.7ml, and 30 mg of sucrose as a bait was placed on it. Ten female adultsof Musca domestics (house fly) were set free in the polyethylene cup,which was then kept covered. After 24 hours, their survival was examinedto determine the mortality.

[0853] As a result, in the treatment with each of the compoundsdescribed above, it was exhibited the mortality of 100%.

TEST EXAMPLE 6 Pesticidal Test Against German cockroach

[0854] Each formulation of the compound 1, 2, 3, 4, 5, 9, 10, 11, 12,15, 16, 17, 23, 30, 31, 32, 33, 36, 39, 40, 41, 42, 43, 46, 47, 52, 55,56, 57, 58, 59, 60, 64, 68, 69, 74, 79, 84, 89, 102, 109, 110, 114, 119,120 and 121 obtained in Formulation Example 5 was diluted with water sothat the active ingredient concentration came to 500 ppm to prepare atest liquid for each compound.

[0855] On the bottom of a polyethylene cup of 5.5 cm in diameter wasplaced a filter paper on the same size, to which the test liquid hadbeen prepared as described above, was added dropwise in an amount of 0.7ml, and 30 mg of sucrose as a bait was placed on it. Two male adults ofGerman cockroach (Blattalla germanica) were set free in the polyethylenecup, which was then kept covered. After 6 days, their survival wasexamined to determine the mortality.

[0856] As a result, in the treatment with each of the compoundsdescribed above, it was exhibited the mortality of 100%.

Test Example 7 Pesticidal Test Against Cullex pipiens pallens

[0857] Each formulation of the compound 1, 2, 3, 4, 5, 6, 7, 9, 10, 11,12, 13, 15, 16, 17, 19, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 52, 54,55, 56, 57, 58, 59, 60, 61, 63, 64, 65, 66, 67, 68, 69, 70, 71, 74, 75,76, 78, 79, 80, 81, 82, 83, 84, 89, 91, 92, 97, 98, 99, 100, 101, 102,103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 115, 116, 118 and121 obtained according to Formulation Example 5 was diluted with waterso that the active ingredient concentration came to 500 ppm to prepare atest liquid for each compound.

[0858] In 100 ml of ion-exchanged water, the test liquid had beenprepared as described above, was added dropwise in an amount of 0.7 ml(the concentration of active ingredient was 3.5 ppm). Twentyfinal-instar larvae of Cullex pipiens pallens (common mosquito) were setfree in the solution. After 1 days, their survival was examined todetermine the mortality. As a result, in the treatment with each of thecompounds described above, it was exhibited the mortality of 100%.

INDUSTRIAL APPLICABILITY

[0859] The present invention makes it possible to effectively controlpests such as insect pests, acarine pests, and nematode pests.

1. A pesticide composition comprising a malononitrile compound offormula (X):

wherein R¹ and R² are the same or different and independently C₁-C₅(halo)alkyl, C₁-C₅ (halo)alkyloxy, C₂-C₅ (halo)alkenyl, C₂-C₅(halo)alkynyl, hydrogen, or cyano; R³ and R⁴ are the same or differentand independently C₁-C₁₀ alkyl, C₂-C₁ alkenyl, C₂-C₁₀ alkynyl, orhydrogen, or R³ and R⁴ are taken together to form C₂-C₆ (halo)alkyleneor C₄-C₆ (halo)alkenylene; R⁵ is halogen, cyano, nitro, C₁-C₄(halo)alkyl, C₂-C₄ (halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄(halo)alkyloxy, C₁-C₄ (halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄(halo)alkylsulfonyl, C₁-C₄ (halo)alkylcarbonyl, C₁-C₄(halo)alkyloxycarbonyl, C₁-C₄ (halo)alkylcarbonyloxy, phenyloxy, orphenylthio, in which the phenyloxy and phenylthio groups may optionallybe substituted with halogen or C₁-C₃ alkyl; n is an integer of 0 to 4;R⁶ is hydrogen, halogen, cyano, nitro, C₁-C₄-(halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl; or R⁵ and R⁶ are taken together to form methylenedioxy;with the provisos that when R⁶ is hydrogen, then n is an integer of 1 to4 and that when n is 2 or more, then R⁵'s are the same or different fromeach other; as an active ingredient, and a carrier.
 2. The pesticidecomposition according to claim 1, wherein a containing amount of themalononitrile compound is 0.1% to 95% by weight.
 3. A pest controllingmethod comprising applying an pesticidally effective amount of amalononitrile compound of formula (X):

wherein R¹ and R² are the same or different and independently C₁-C₅(halo)-alkyl, C₁-C₅ (halo)alkyloxy, C₂-C₅ (halo)alkenyl, C₂-C₅(halo)alkynyl, hydrogen, or cyano; R³ and R⁴ are the same or differentand independently C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, orhydrogen, or R¹ and R⁴ are taken together to form C₂-C₆ (halo)alkyleneor C₄-C₆ (halo)alkenylene; R⁵ is halogen, cyano, nitro, C₁-C₄(halo)alkyl, C₂-C₄ (halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄(halo)alkyloxy, C₁-C₄ (halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄(halo)alkylsulfonyl, C₁-C₄ (halo)alkylcarbonyl, C₁-C₄(halo)alkyloxycarbonyl, C₁-C₄ (halo)alkylcarbonyloxy, phenyloxy, orphenylthio, in which the phenyloxy and phenylthio groups may optionallybe substituted with halogen or C₁-C₃ alkyl; n is an integer of 0 to 4;R⁶ is hydrogen, halogen, cyano, nitro, C₁-C₄ (halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl; or R⁵ and R⁶ are taken together to form methylenedioxy;with the provisos that when R⁶ is hydrogen, then n is an integer of 1 to4 and that when n is 2 or more, then R⁵'s are the same or different fromeach other; to pests or habitats of pests.
 4. The pest controllingmethod according to claim 3, wherein R⁶ is halogen, cyano, nitro, C₁-C₄haloalkyl, C₁-C₄ haloalkyloxy or C₁-C₄ haloalkylthio.
 5. The pestcontrolling method according to claim 3, wherein R³ and R⁴ are the sameor different and independently C₁-C₅ alkyl, C₂-C₅ alkenyl, C₂-C₅alkynyl, or hydrogen, or R³ and R⁴ are taken together to form C₂-C₆(halo)alkylene.
 6. The pest controlling method according to claim 3,wherein R¹ and R² are both hydrogen.
 7. The pest controlling methodaccording to claim 3, wherein R¹ and R² are the same or different andindependently C₁-C₃ (halo)alkyl, C₁-C₃ (halo)alkyloxy, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, hydrogen, or cyano; R⁵ and R⁶ arethe same or different and independently halogen, cyano, nitro, C₁-C₃haloalkyl, C₁-C₈ haloalkyloxy, C₁-C₃ (halo)alkylthio, C₁-C₃(halo)alkylsulfinyl, C₁-C₃ (halo)alkylsulfonyl, C₁-C₃(halo)alkylcarbonyl, or C₁-C₃ haloalkyloxycarbonyl.
 8. The pestcontrolling method according to claim 7, wherein R³ is hydrogen and R⁴are vinyl, allyl, ethyl, 3-butenyl and 1-propenyl.
 9. The pestcontrolling method according to claim 3, wherein the pests are insectpests.
 10. Use of a malononitrile compound of formula (X):

wherein R¹ and R² are the same or different and independently C₁-C₅(halo)alkyl, C₁-C₅ (halo)alkyloxy, C₂-C₅ (halo)alkenyl, C₂-C₅(halo)alkynyl, hydrogen, or cyano; R³ and R⁴ are the same or differentand independently C₁-C₁₀ alkyl, C₂-C₁₀ alkenyl, C₂-C₁₀ alkynyl, orhydrogen, or R³ and R⁴ are taken together to form C₂-C₆ (halo)alkyleneor C₄-C₆ (halo)alkenylene; R⁵ is halogen, cyano, nitro, C₁-C₄(halo)alkyl, C₂-C₄ (halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄(halo)alkyloxy, C₁-C₄ (halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄(halo)alkylsulfonyl, C₁-C₄ (halo)alkylcarbonyl, C₁-C₄(halo)alkyloxycarbonyl, C₁-C₄ (halo)alkylcarbonyloxy, phenyloxy, orphenylthio, in which the phenyloxy and phenylthio groups may optionallybe substituted with halogen or C₁-C₃ alkyl; n is an integer of 0 to 4;R⁶ is hydrogen, halogen, cyano, nitro, C₁-C₄ (halo)alkyl, C₂-C₄(halo)alkenyl, C₂-C₄ (halo)alkynyl, C₁-C₄ (halo)alkyloxy, C₁-C₄(halo)alkylthio, C₁-C₄ (halo)alkylsulfinyl, C₁-C₄ (halo)alkylsulfonyl,C₁-C₄ (halo)alkylcarbonyl, C₁-C₄ (halo)alkyloxycarbonyl, C₁-C₄(halo)alkylcarbonyloxy, phenyloxy, or phenylthio, in which the phenyloxyand phenylthio groups may optionally be substituted with halogen orC₁-C₃ alkyl; or R⁵ and R⁶ are taken together to form methylenedioxy;with the provisos that when R⁶ is hydrogen, then n is an integer of 1 to4 and that when n is 2 or more, then R⁵'s are the same or different fromeach other; as an active ingredient of a pesticide composition.